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Effects of Smoking Temperature, Smoking Time, and Type of Wood

Sawdust on Polycyclic Aromatic Hydrocarbon Accumulation Levels
in Directly Smoked Pork Sausages
Radu C. Racovita, Catinca Secuianu,* Maria D. Ciuca, and Florentina Israel-Roming
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ABSTRACT: Smoking is an excellent food preservation method but also a source of contamination of foodstuffs with carcinogenic
polycyclic aromatic hydrocarbons (PAHs). Herein we investigated the influence of smoking temperature, smoking time, and type of
wood sawdust used as smoke source on PAH levels attained through controlled smoking of pork sausages. Four PAHs
Downloaded via 171.252.153.213 on March 28, 2023 at 10:12:56 (UTC).

(benz[a]anthracene, chrysene, benzo[b]fluoranthene, benzo[a]pyrene) were monitored, as required by European Commission

Regulation 835/2011. PAH concentrations increased continuously both with higher temperatures (55−95 °C) and with longer
smoking periods (2−9 h), although the level of benzo[a]pyrene exhibited a tendency to plateau after 6 h. Among seven types of
hardwoods tested, plum, alder, and birch yielded PAH concentrations considerably higher than that of commonly used beech, and
oak showed similar levels to beech while apple and, to a lesser extent, walnut caused lower levels of sausage contamination. These
findings could guide the establishment of good practices in the smoked meat industry.
KEYWORDS: polycyclic aromatic hydrocarbon, gas chromatography−mass spectrometry, smoked pork sausage, smokehouse temperature,
smoking time, type of wood

1. INTRODUCTION contamination levels of food products.12 In response, the

In addition to drying and salting, smoking is a third European Commission (EC) adopted Regulation No. 835/
preservation method commonly used for meat and fish, 2011 that sets the upper limits acceptable for BaP and PAH4
among other foods, and dates as far back as 90 000 years concentrations in various categories of retail foodstuffs
ago.1 The significant extension of a food product’s shelf life marketed within the European Union (EU).13
through smoking is the result of the combined action of several Efforts geared toward correlating PAH accumulation in
phenolics native to smoke that are transferred to the foodstuff.1 smoked foods with technical aspects of the smoking process
Many of these phenolics were proven, in experiments have been made in various laboratories around the world.
replicating smoke compositions, to have antioxidant,2 anti- Among factors that have been found to influence to a higher or
fungal,3 and antimicrobial properties.4 Furthermore, smoking is lesser degree the levels of PAHs reached in the smoked end-
associated with additional organoleptic benefits: it enhances product are the method of smoke generation, such as wood
the visual appearance of meats, through browning reactions smoldering, thermostated plates, friction, or steam smoking,1,14
between meat amino acids and carbonyl compounds derived the way of combustion of wood material, whether by ignition
from thermal transformations of wood carbohydrates, and from a flame or by direct heating,15 the specific smoking
imparts a characteristic smoky smell and flavor, for which a technique employed, i.e., industrial or traditional,16 direct or
combination of phenolics, carbonyls, and lactones have been indirect,17−20 hot or cold,18,21 classic or using liquid
shown to be responsible.1 On the other hand, smoking also smoke,14,21,22 smoke generation temperature,6,8,14 the position
causes significant contamination of foodstuffs with known or of food material in the smokehouse,10,19,23 the duration of
suspected carcinogens and mutagens, such as formaldehyde,1 smoking,7,18,24,25 and the specific type of fuel used to generate
heterocyclic amines,5 and especially polycyclic aromatic smoke, including various kinds of wood,6,8,17,18,26 charcoal,20,26
hydrocarbons (PAHs).6−10 The latter are formed through or sugar.24
incomplete pyrolysis of the organic fuel (typically wood) used Aside from smoked plant and animal foods,27 several other
to generate smoke and can raise serious health concerns at high studies were published in recent years focusing on a wide range
levels of ingestion.11
Consequently, in 2008, the Panel on Contaminants in the
Food Chain (CONTAM Panel) of the European Food Safety Received: July 2, 2020
Authority (EFSA) made a recommendation that the Revised: August 4, 2020
cumulative concentration of benzo[a]pyrene (BaP), chrysene Accepted: August 7, 2020
(CHR), benz[a]anthracene (BaA), and benzo[b]fluoranthene Published: August 7, 2020
(BbF) denoted as PAH4, in addition to the individual
concentration of BaP, be used as best indicator of PAH

© 2020 American Chemical Society https://dx.doi.org/10.1021/acs.jafc.0c04116

9530 J. Agric. Food Chem. 2020, 68, 9530−9536
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of food products contaminated with PAHs either from which was typically every 20−30 min. Sausages were smoked with
environmental sources or through certain processing tech- smoldering beech sawdust (i) for a fixed duration of 3 h at five
nologies. These included, among others, bread that was toasted different temperatures (55 °C/328 K, 65 °C/338 K, 75 °C/348 K, 85
in various ways,28 plant foods harvested from the vicinity of a °C/358 K, and 95 °C/368 K) and (ii) for various durations (2, 3, 5, 6,
8, and 9 h) at a fixed temperature of 75 °C, the latter temperature
recent chemical company fire,29 animal feed ingredients,30 being recommended for smoking sausages in the smokehouse user’s
instant coffee,31 alcoholic drinks,32 canned bivalves in pickle manual. With the other types of sawdust, smoking was performed at
and natural sauce,33 fish oils,34,35 and grilled pork marinated the recommended temperature (75 °C) and for fixed amounts of time
with beer marinades.36 (2, 3, 5, 6, 8, and 9 h, respectively). After the desired smoking time,
In the present work, we investigated the influence of smoked sausages were removed from the smokehouse using clean
smokehouse temperature, duration of smoking, and type of metal tongs and were allowed to cool to room temperature before
wood sawdust used as fuel for smoke generation on BaP and being processed as described in section 2.5. Each smoking experiment
total PAH4 contamination levels of pork sausages obtained by (at a certain temperature, for a certain amount of time, and using a
direct smoking. In the context of food safety and quality certain type of sawdust) was repeated three times on different days
using roughly equal-sized raw sausages.
assurance, the findings of this study serve, along with the
2.5. Preparation of Smoked Sausage Samples for GC-MS
relatively few other studies on this topic mentioned above, as Analysis. In a typical experiment, smoked sausages were minced and
valuable reference data and scientific basis for defining best homogenized in a Z-1111-O bowl chopper (Zephyr S.L.G.,
practices for the food smoking industry. Germany). About 10 g (weighed to a precision of ±0.1 mg using a
KERN ADB 200-4 analytical balance) of finely minced sample was
2. MATERIALS AND METHODS transferred into the 50 mL QuEChERS extraction tube along with 10
2.1. Chemicals. Acetonitrile (≥99.9%, HPLC grade) was acquired mL of water and 10 mL of acetonitrile. Samples were intensely
from Scharlab S.L. (Spain) and used as-received. Water from a Milli- agitated at 2500 rpm using a DLAB MX-S vortex (Dragon Lab,
Q Reference Water Purification System (18 MΩ cm resistivity) was China) for 1 min and then centrifuged at 2720g for 5 min in a
used in all experiments. Helium (≥99.9999%) and nitrogen Medibas+ centrifuge (Auxilab S.L., Spain). Five milliliters from the
(≥99.996%) were purchased from Linde GmbH (Germany). acetonitrile layer was transferred to a 15 mL QuEChERS tube for
QuEChERS (Quick-Easy-Cheap-Effective-Rugged-Safe) kits for purification by dSPE. Stirring and centrifugation steps were repeated.
PAH extraction from the food matrix were from Thermo Fisher After settling, 1.5 mL of sample was transferred into a 2 mL GC
Scientific Inc. (USA) and, in essence, were 50 mL conical tubes amber vial (ISOLAB GmbH, Germany), 10 μL of an acetonitrile
containing 6 g of anhydrous magnesium sulfate and 1.5 g of sodium solution of internal standard (ABaP) of exact concentration was
acetate. QuEChERS kits for purification of PAHs by dispersive solid- added, and then the sample was evaporated to dryness under a gentle
phase extraction (dSPE) came from Agilent Technologies Inc. (USA) stream of N2 at 50 °C and redissolved with fresh acetonitrile up to a
and were 15 mL conical tubes with 400 mg of PSA (primary- volume of 100 μL in 150 μL vial inserts (Agilent Technologies Inc.,
secondary amine), 400 mg of octadecyl-substituted silica, and 1200 Lexington, MA). For GC-MS analysis, a 1 μL aliquot of the resulting
mg of anhydrous magnesium sulfate. For gas chromatography−mass solution was injected into the GC inlet.
spectrometry (GC-MS) method development and validation, a 2.6. Quantification of PAHs in Smoked Sausages by GC-MS.
certified reference material (CRM) from Ultra Scientific Inc. (now A Thermo Scientific Focus GC with a Polaris Q ion trap MS detector
Agilent Technologies Inc.), JTB-0005, consisting of a 16 PAH mixture was used. Sample injections were performed in splitless mode, using a
including PAH4, was used. Another CRM, BCR-092, i.e., neat 10- TriPlus Autosampler interfaced with the GC, at an injector
azabenzo[a]pyrene (ABaP) (≥99.6%), acquired from LGC Limited temperature of 250 °C (523 K). A TR-5MS column from Thermo
(United Kingdom), served as internal standard for GC measurements. Fisher Scientific (30 m long, 0.25 mm i.d., 0.25 μm film thickness)
2.2. Wood Sawdust. For studying the effect of smoking was employed. Helium at a flow rate of 1 mL/min was the mobile
temperature and time on PAH4 accumulation in pork sausages, phase. The MS ion source temperature was 250 °C (523 K), and the
beech wood sawdust purchased from RIA DO Trading S.R.L. transfer line was set at 280 °C (553 K). The temperature program was
(Romania) was used in all experiments. To assess the effect of the as follows: 1 min hold at 70 °C (343 K); ramp 10 °C/min to 300 °C
type of sawdust used to generate smoke, five other types of wood (573 K); 10 min hold. All measurements were performed in single ion
sawdust (apple, plum, birch, oak, walnut) were acquired from monitoring (SIM) mode, for increased sensitivity, using the following
Axtschlag GmbH (Germany) and an additional one (alder) from m/z characteristic ratios: 228 (BaA), 228 (CHR), 252 (BbF), 252
Jaxon Sp. z o.o. (Poland). (BaP), 252 (ABaP).
2.3. Pork Sausages. The raw sausages used for smoking under 2.7. GC-MS Method Validation. The method was validated
controlled conditions consisted of ground pork in natural hog casing intralaboratory in agreement with EC Regulation No. 836/2011.37
and were purchased from a major retailer in Romania. All had the Accordingly, calibration curves for peak areas as a function of
same batch number and were frozen immediately after purchase. They individual PAH concentration were obtained and found to be linear
were stored in frozen state at −18 °C (255 K) for no more than 1 over 4 orders of magnitude (10−4− 1 μg/mL) in the case of BaA,
month. For smoking experiments, a sufficient number of sausages CHR, and BaP, and 3 orders of magnitude (10−3− 1 μg/mL) in the
were removed from the freezer and left to thaw in a fridge at 4 °C case of BbF, respectively. Analytical sensitivities Si, i.e., the slopes of
(277 K) for about 24 h prior to use. calibration lines for each analyte i, were, in the following order: 3.73 ×
2.4. Smoking of Sausages. A Direca Depo Professional 105 (BaA), 5.78 × 105 (CHR), 3.18 × 105 (BbF), and 3.76 × 105
Smokehouse with four racks (Direca Depo S.R.L., Romania) and (BaP). The limits of detection, LOD, and quantification, LOQ, were
double walls with mineral wool insulation was used in all sausage determined as LODi = 3σi/Si and LOQi = 10σi/Si, where σi and Si are
smoking experiments. It is equipped with temperature control for the the standard deviation of the mean peak area obtained using a series
smoking chamber, timer, a metal pan for sawdust heated by an electric of 20 blanks for analyte i and the sensitivity, respectively. LODs
heating coil (i.e., smoke generator), a lateral sawdust feeder for obtained were as follows: 0.093 (BaA), 0.070 (CHR), 0.058 (BbF),
replenishing sawdust when needed, and a smoke exhaust at the top and 0.083 μg/kg (BaP), while LOQs were found to be 0.309 (BaA),
with adjustable opening. In all experiments, raw sausages were placed 0.232 (CHR), 0.195 (BbF), and 0.275 μg/kg (BaP), respectively. All
at the same height level as the temperature sensor of the smokehouse, LODs were below 0.3 μg/kg and all LOQs below 0.9 μg/kg as
namely on the uppermost rack, i.e., farthest from the smoke generator. required for in-house validation.37 As all replicates of raw pork
The smoke exhaust was kept in the completely open position, and sausages analyzed using the same procedure described in section 2.5
new portions of 15 g of sawdust, moistened with 5 mL of water, were for smoked sausages exhibited undetectable levels (<LOD) for all four
added every time the flow rate of the exhaust decreased substantially, PAHs, they were used as matrixes for recovery assessments. In these

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experiments, the same protocol described in section 2.5 was used, The total concentration of PAH4 showed an almost linear
with the only additional step that the 10 g of minced raw sausage was increase with temperature, within error limits. The concen-
spiked with 200 μL of a PAH solution obtained by diluting 1 mL of tration of BaP alone also increased, albeit less regularly, the
JTB-0005 CRM with 9 mL of acetonitrile. Percent recoveries of most significant increases being from 55 °C to 65 °C and then
spiked amounts, given as averages of three replicates, were found to be
in the following order: 60.1 (BaA), 58.8 (CHR), 67.6 (BbF), and
from 75 °C to 85 °C. Notably, only for sausage samples
65.4% (BaP), and were thus within the 50−120% range stipulated by smoked for 3 h at the lowest temperature, 55 °C, were the
EC Regulation 836/2011.37 For precision testing, Horwitz ratios concentrations of BaP and PAH4 found below the EC-
HORRATR were calculated for each EC-regulated PAH by division of imposed limits of 2 and 12 μg/kg, respectively.13
relative standard deviations of the mean concentrations determined Overall, a 40 °C temperature increase (from 55 °C to 95
for each analyte in the same spiked samples with the predicted value °C) triggered a more than 3-fold increase of both BaP and
of 22% given by the modified Horwitz equation for trace analysis.38 In PAH4 contents, demonstrating that smokehouse temperature
order, they were found to be 0.277 (BaA), 0.214 (CHR), 0.948 has a major effect on foodstuff contamination during smoking.
(BbF), and 0.437 (BaP), and were therefore all well below the upper Increases of PAH concentrations with smoking temperature
limit of 2.37
2.8. Statistical Analysis. A randomized experimental design was
are not surprising and were expected, given that PAHs are
used considering the fixed effect of each type of smoking treatment produced through thermal treatment of organic matter,
and random effect of replicate within independent groups of raw including foodstuffs.12 Such temperature-induced increases
sausages as the experimental unit. All PAH concentration data have been reported previously in the literature for smoked
measured were subjected to one-way analysis of variance (ANOVA). fish,18 as well as for smoked meat.19,39
Significant pairwise differences resulting from a given treatment 3.2. Effect of Smoking Time on PAH Concentrations.
variable (temperature, time, or type of wood sawdust) were tested Smoking time also had a strong influence on PAH
using Student’s two-sided t test. A calculated p value below 0.05 was accumulation in pork sausages (Figure 2). The total
considered to be statistically significant. All PAH concentrations were
reported as mean value ± standard deviation. Statistical analysis
procedures were carried out using Microsoft Excel (part of Microsoft
Office Suite 365, Redmond WA).

3. RESULTS AND DISCUSSION

Concentrations of the four PAHs in the whole smoked
sausages were determined individually and compared (i) as a
function of smoking temperature when beech sawdust was
used for a fixed smoking time; (ii) as a function of smoking
time when beech sawdust was used at a fixed temperature; (iii)
as a function of the type of wood sawdust used to produce
smoke at a constant temperature for fixed durations.
3.1. Effect of Smoking Temperature on PAH
Concentrations. Aside from some minor fluctuations, all
PAH concentrations showed a generally increasing trend as
smoking temperature increased (Figure 1). Irrespective of Figure 2. Variation of individual concentrations of BaP, BaA, CHR,
temperature, the highest concentration was always that of and BbF and the sum of their concentrations (PAH4) in smoked
CHR, followed by BaA and BaP, BbF being the least abundant. sausages as a function of smoking time (smoke source: beech wood
sawdust, smoking temperature: 75 °C). Error bars correspond to
standard deviations of the mean (n = 3). Identical letters with the
same color indicate that there is no significant difference for different
smoking times (two-tailed t test, p < 0.05).

concentration of PAH4 and that of the most abundant of all

PAHs, i.e. CHR, exhibited continuous increases over the
course of the first 8 h of smoking and only in the last hour no
longer increased significantly, although it cannot be excluded
that the increase would have continued had the smoking
process not been ceased after 9 h. The concentrations of BaP
and BaA also increased for the first 6 h of smoking, after which
they came to a halt. This could be due to substantial loss of the
lipid fraction in the sausage through dripping by this time
point, as BaP and PAH4 contents in smoked sausages have
been previously reported to vary proportionally to fat
content.10,21,40 The increase in BaP concentration was more
Figure 1. Variation of individual concentrations of benzo[a]pyrene significant, such that after 5 and 6 h of direct smoking, BaP
(BaP), benz[a]anthracene (BaA), chrysene (CHR), and benzo[b]-
fluoranthene (BbF) and the sum of their concentrations (PAH4) in
became roughly equally abundant as BaA. BbF was least
smoked sausages as a function of smoking temperature (smoke abundant of all PAHs at any time, the only notable increase in
source: beech wood sawdust, smoking time: 3 h). Error bars its concentration being recorded between 3 and 5 h of smoking
correspond to standard deviations of the mean (n = 3). Identical time, after which it also remained roughly constant. Once
letters with the same color indicate there is no significant difference again, it was found that even after only 2 h of smoking at 75
for different smoking temperatures (two-tailed t test, p < 0.05). °C, the EC limits for BaP and PAH4 were both exceeded.
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Past investigations in the literature on the effect of increasing birch sawdust, and they were all significantly higher than in the
smoking time also showed increases of PAH contents of case of beech sawdust (Figure 3). The wood of the other
smoked foodstuffs, in some studies with certain time points Fagaceae species, oak, caused similar levels of BaP as beech,
beyond which further increases were no longer observed, either while apple was always associated with lower levels of BaP in
for BaP alone7 or for the sum of all PAHs,18 and in others with the final food product. Walnut also showed comparatively
no obvious tendency for concentrations to level off even after 5 lower BaP levels not only for the first 3 h, but also up to 6 h of
h of smoking meat.19 In any case, our data clearly showed that smoking, yet at longer times it reached levels similar to beech,
a 3-fold increase in smoking time (from 2 to 6 h) determined a as BaP concentration did not level off as early as it did for
3-fold increase of BaP concentration and more than 2-fold beech (Tables S1−S6).
increase of total PAH4, proving that smoking duration also has BaA followed a very similar trend, with significantly higher
an important impact on PAH accumulation in foods. concentrations than for beech in the cases of alder, birch, and
3.3. Effect of Type of Wood Sawdust on PAH especially plum wood. Oak- and walnut-smoked sausages
Concentrations. The types of sawdust used in the experi- exhibited comparable or only slightly higher levels of BaA to
ments spanned a wide range of hardwoods, specifically from that of beech, while apple sawdust was the only to yield a
seven tree species commonly used in the smoking process. consistently lower BaA contamination level at all smoking
These species included members of the Fagaceae family (beech times (Figure 3 and Tables S1−S6).
and oak), the Betulaceae family (alder and birch), the As far as the most abundant PAH is concerned, CHR, its
Juglandaceae family (walnut), and the Rosaceae family level was highest for plum, followed by the two Betulaceae
(apple and plum). species, alder and birch, in this order, while the remainder of
For a smoking duration of 3 h at a constant temperature of wood types investigated had very similar levels of contami-
75 °C, the concentrations of PAHs varied widely depending on nation with CHR (Figure 3 and Tables S1−S6).
the type of wood sawdust used (Figure 3). Beech wood is the With respect to the least abundant PAH, i.e. BbF, the same
most common hardwood used for smoking meat products,9 so variation as for CHR was observed, except that apple wood-
it was taken as reference for comparisons here. induced levels of BbF were found significantly lower than those
caused by beech, but only within the first 3 h (Figure 3 and
Tables S1−S6).
Most importantly, total PAH4 concentration varied greatly
as a function of sawdust used as fuel. Compared to beech
sawdust, sausages smoked with plum sawdust had a total
PAH4 level almost five times greater, while alder and birch
showed roughly 50% and 25% increases, respectively, within 3
h of smoking (Figure 3). Longer duration augmented these
differences (Tables S1−S6). There was no significant differ-
ence between beech and oak at any time, and for walnut only a
slight decrease (ca. 10%) was recorded for the first 3 h (Figure
3), which disappeared at longer times (Tables S1−S6). Finally,
apple wood showed a substantial (ca. 25−30%) decrease in
PAH4 level as compared to beech at all smoking times (Figure
3 and Tables S1−S6). Even so, only for the first 2 h of smoking
Figure 3. Variation of individual concentrations of BaP, BaA, CHR,
was this level below the EC limit of 12 μg/kg (Table S1).
and BbF and the sum of their concentrations (PAH4) in smoked These data show some degree of correlation between PAH
sausages as a function of the type of wood sawdust used to generate accumulation levels in sausages during direct, hot smoking with
smoke (smoking temperature: 75 °C, smoking time: 3 h). Error bars wood sawdust and the families to which the trees belong to, in
correspond to standard deviations of the mean (n = 3). Identical the sense that Betulaceae species (alder and birch) showed
letters with the same color indicate that there is no significant consistently higher PAH concentrations than Fagaceae species
difference for different types of wood sawdust (two-tailed t test, p < (beech and oak). However, representatives of the Rosaceae
0.05). family were at opposite poles, as plum wood yielded the
highest levels of PAH contamination and apple the lowest;
In terms of relative abundance of the four PAHs, just like in therefore, such correlations are limited. An alternative
the case of beech discussed in sections 3.1 and 3.2, CHR was correlation could be in terms of lignin content of respective
the most abundant and BbF was least abundant among PAH4 wood types, as lignin is an already aromatic precursor to
for the other six types of sawdust as well. BaP was generally PAHs,41 so a higher lignin content may correlate with higher
third most abundant, however, with levels as low as that of BbF intake of PAHs into smoked meats. Indeed, compared to lignin
in the cases of apple, walnut, and oak woods. BaA was mass content of beech wood, which is around 22%,42 apple
consistently more abundant than BaP irrespective of wood type wood was reported to have about 1% lower lignin content,43
and, in the cases of plum and oak woods, it reached while plum wood was shown to have a substantially larger
concentration levels as high as those of CHR after 3 h of lignin portion in its structure, at about 32−33%,44 which
smoking at 75 °C (Figure 3). Supporting Information Tables correlates well with the much higher levels of all PAHs
S1−S6 show, in addition, that the relative distributions of the observed in sausages smoked with plum sawdust. The
four PAHs in the PAH4 mixture remained the same for other correlation also stands for walnut (20−22% lignin)45 and
smoking times too, within error limits. oak (with highly variable reported lignin content, 17−30%),46
After 3 h of smoking, the highest concentrations of BaP in given that some PAH levels were lower and others equal for
smoked sausages were caused, in order, by plum, alder, and these two wood types as compared to beech, but is not as good
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J. Agric. Food Chem. 2020, 68, 9530−9536
Journal of Agricultural and Food Chemistry pubs.acs.org/JAFC Article

with respect to alder (ca. 22% lignin) and birch (18−20% wood sawdust used that were attained after 2, 3, 5, 6, 8,
lignin).45 and 9 h, respectively, of controlled smoking at 75 °C.
Somewhat similar trends have been reported in the few past Figure S1 showing an example of a typical gas
studies on wood type effect on PAHs in smoked meat chromatogram (PDF)

■
products, although these used predominantly other kinds of
wood.6,8,26 Malarut and Vangnai8 compared, among other AUTHOR INFORMATION
properties, the PAH contents of sausages smoked with beech
Corresponding Author
woodchips against four other tree species native to Southeast
Asia (neem, copper pod, earleaf acacia, and eucalypt), all very Catinca Secuianu − University “Politehnica” of Bucharest,
different from the species studied in the present work, so Faculty of Applied Chemistry and Materials Science,
comparisons cannot be made. Hitzel et al.6 investigated PAH Department of Inorganic Chemistry, Physical Chemistry and
accumulation levels in Frankfurter-type sausages (made of pork Electrochemistry, Bucharest 011061, Romania; Imperial College
and beef) and minisalamis (pork) when smoked with a London, Department of Chemical Engineering, London SW7
selection of hardwood chips (oak, poplar, hickory, alder, 2AZ, United Kingdom; orcid.org/0000-0001-5779-6415;
beech) and softwood chips (spruce and fir), respectively. Email: [email protected], [email protected]
Similar to our results, they also observed an increase of both Authors
BaP and PAH4 concentrations when smoking sausages with Radu C. Racovita − University “Politehnica” of Bucharest,
alder as compared to beech, but they also noted a sensible Faculty of Applied Chemistry and Materials Science,
decrease of BaP and PAH4 levels in both sausages and Department of Inorganic Chemistry, Physical Chemistry and
minisalamis when using oak woodchips. On the contrary, Electrochemistry, Bucharest 011061, Romania; orcid.org/
Stumpe-Viksna et al.26 observed the second lowest BaP and 0000-0002-6396-9869
total PAH levels in pork smoked with alder wood in a series of Maria D. Ciuca − University “Politehnica” of Bucharest, Faculty
smoking experiments using 10 different types of wood: apple, of Applied Chemistry and Materials Science, Department of
alder, alder + juniper, spruce, maple, hazel, plum, aspen, bird- Inorganic Chemistry, Physical Chemistry and Electrochemistry,
cherry, and rowantree. Their species selection did not include Bucharest 011061, Romania; orcid.org/0000-0001-5530-
beech, but still, in agreement with our findings, they also 0439
recorded the lowest BaP and cumulative PAH levels for apple Florentina Israel-Roming − University “Politehnica” of
wood and about seven times higher levels for plum, which was Bucharest, Faculty of Applied Chemistry and Materials Science,
the second worst choice of wood in their study, after spruce. Department of Inorganic Chemistry, Physical Chemistry and
Addition of juniper to alder wood during smoking resulted in Electrochemistry, Bucharest 011061, Romania; University of
two to three times higher concentrations of the four PAHs, so, Agronomic Sciences and Veterinary Medicine, Biotechnology
considering that spruce and juniper are both softwoods, known Department, Bucharest 011464, Romania
to have higher levels of lignin in their composition in
comparison to hardwoods,45 it follows that there may indeed Complete contact information is available at:
be a relationship between the lignin content of a certain type of https://pubs.acs.org/10.1021/acs.jafc.0c04116
wood and the level of PAHs transferred to meat products
during smoking with sawdust from that wood. Funding
As a recommendation for the smoked meat products This work was supported by a grant of Ministry of Research
industry, it follows from this work that cold (15−25 °C) or and Innovation, CNCS - UEFISCDI, project number PN-III-
warm (25−50 °C) smoking techniques are more desirable to P1-1.1-PD-2016-0934, within PNCDI III.
avoid high contamination levels with PAH4, because the Notes
The authors declare no competing financial interest.

■
higher the smoking temperature the higher the concentrations
of PAHs will be in the end product. Smoking time should also
be kept to a minimum that is still acceptable for sensory ACKNOWLEDGMENTS
properties, because even though some of the PAHs may level The authors are grateful to Dr. Maria Mihaly (University
off after at a certain time point in the smoking process (6 to 8 “Politehnica” of Bucharest) for access to instrumentation,
h in this work), others may still continue to accumulate in the CRMs provided, and many fruitful discussions.
smoked foodstuff. In terms of choice of wood sawdust for
smoking, apple and walnut sawdust seem better options, as
they reduce somewhat the PAH content in comparison to the
■ ABBREVIATIONS
ABaP, 10-azabenzo[a]pyrene; ANOVA, analysis of variance;
staple beech wood used by the smoking industry. Oak wood BaA, benz[a]anthracene; BaP, benzo[a]pyrene; BbF, benzo-
appears equally suitable as its Fagaceae relative, and plum and [b]fluoranthene; CHR, chrysene; CRM, certified reference
Betulaceae species, like birch and alder, should be avoided, as material; dSPE, dispersive solid-phase extraction; EC, Euro-
they consistently tend to yield higher PAH concentrations in pean Commission; EFSA, European Food Safety Authority;
smoked foods. EU, European Union; g, gravitational acceleration; GC-MS, gas

■
*
ASSOCIATED CONTENT
sı Supporting Information
chromatography−mass spectrometry; HORRATR, Horwitz
ratio (for reproducibility); HPLC, high performance liquid
chromatography; LOD, limit of detection; LOQ, limit of
The Supporting Information is available free of charge at quantification; QuEChERS, Quick-Easy-Cheap-Effective-
https://pubs.acs.org/doi/10.1021/acs.jafc.0c04116. Rugged-Safe; PAH, polycyclic aromatic hydrocarbon; PAH4,
sum of benz[a]anthracene, benzo[a]pyrene, benzo[b]-
Tables S1−S6 showing comparative concentrations of fluoranthene, chrysene; PSA, primary-secondary amine; SIM,
BaP, BaA, CHR, BbF, and total PAH4 for every type of single ion monitoring
9534 https://dx.doi.org/10.1021/acs.jafc.0c04116
J. Agric. Food Chem. 2020, 68, 9530−9536
Journal of Agricultural and Food Chemistry

■
pubs.acs.org/JAFC Article

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