Polycyclic Aromatic Compounds

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Polycyclic Aromatic Compounds

ISSN: (Print) (Online) Journal homepage: https://www.tandfonline.com/loi/gpol20

Concentrations and Risk of Polycyclic Aromatic


Hydrocarbons (PAHs) in Oil and Tomato-Based
Sauces from Selected Brands of Canned Fish
Consumed in Nigeria

Chukwujindu M. A. Iwegbue, Godswill O. Tesi, Anthony A. Ogbuta,


Bulouebibo Lari, Ufuoma A. Igbuku, Grace Obi & Bice S. Martincigh

To cite this article: Chukwujindu M. A. Iwegbue, Godswill O. Tesi, Anthony A. Ogbuta,


Bulouebibo Lari, Ufuoma A. Igbuku, Grace Obi & Bice S. Martincigh (2021): Concentrations
and Risk of Polycyclic Aromatic Hydrocarbons (PAHs) in Oil and Tomato-Based Sauces from
Selected Brands of Canned Fish Consumed in Nigeria, Polycyclic Aromatic Compounds, DOI:
10.1080/10406638.2021.1934046

To link to this article: https://doi.org/10.1080/10406638.2021.1934046

View supplementary material Published online: 21 Jun 2021.

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POLYCYCLIC AROMATIC COMPOUNDS
https://doi.org/10.1080/10406638.2021.1934046

Concentrations and Risk of Polycyclic Aromatic Hydrocarbons


(PAHs) in Oil and Tomato-Based Sauces from Selected Brands
of Canned Fish Consumed in Nigeria
Chukwujindu M. A. Iwegbuea, Godswill O. Tesia,b, Anthony A. Ogbutaa,b, Bulouebibo
Laria,c, Ufuoma A. Igbukua,d, Grace Obie, and Bice S. Martincighf
a
Department of Chemistry, Delta State University, P.M.B., 1, Abraka, Delta State, Nigeria; bDepartment of
Chemical Sciences, University of Africa, Toru-Orua, Bayelsa State, Nigeria; cDepartment of Science Laboratory
Technology, Delta State University, P.M.B. 1, Abraka, Delta State, Nigeria; dDepartment of Science Laboratory
Technology, Delta State Polytechnic, Ozoro, Delta State, Nigeria; eDepartment of Chemistry, Federal University
of Petroleum Resources, Effurun, Delta State, Nigeria; fSchool of Chemistry and Physics, University of
KwaZulu-Natal, Durban, South Africa

ABSTRACT ARTICLE HISTORY


The concentrations of the 16 US EPA polycylic aromatic hydrocarbons (PAHs) Received 21 May 2020
were investigated in oil and tomato-based sauces from some popular brands Accepted 26 February 2021
of canned fish products (mackerel, sardine and tuna) commonly consumed in
KEYWORDS
Nigeria. The aim of the study was to provide data on the PAH compositions
Canned fish; dietary intake;
and likely risks arising from ingestion of these oil and tomato-based sauces. health risk; Nigeria;
The PAH content in these oils and sauces was determined by gas chromatog- PAHs; sauces
raphy-mass spectrometry. The concentrations of PAHs in these samples varied
from 101 to 698 mg kg1 for tomato sauces from canned mackerel, 168 to
733 mg kg1 for oils from canned sardines, and 204 to 459 mg kg1 for oils
from canned tuna. The benzo(a)pyrene and PAH4 (benzo(a)anthracene [BaA]
þ Chrysene [Chry] þ benzo(a)pyrene [BaP] þ benzo(b)fluoranthene [BbF])
concentrations in the majority of the samples exceeded their respective limits
as specified by the European Union regulations. The benzo(a)pyrene carcino-
genic (BaPTEQ) and mutagenic (BaPMEQ) potency values ranged from not
detected (nd) to 288 mg kg1 and nd-217 mg kg1 respectively. The probable
cancer risk arising from consumption of oils and tomato sauces from these
canned fish products were above the acceptable risk value of 106, which
indicates that there is a considerable risk associated with the consumption of
sauces and oils from these canned fish products.

Introduction
Polycyclic aromatic hydrocarbons (PAHs) are pervasive semi-volatile organic pollutants originat-
ing chiefly from incomplete burning of organic materials, including wood, fossil fuels, and plas-
tics, among others. However, PAHs also enter the environment through natural sources such as
forest fires and volcanic eruptions. PAHs consist of two to six fused benzene rings with different
structural arrangements. The prevalence of PAHs in the environment and human foods is a
source of apprehension because of their high toxicity, and carcinogenic, genotoxic and mutagenic
properties, especially exhibited by high molecular weight (HMW) 4–6-ring PAHs. In addition,
PAHs are known to possess endocrine-disrupting properties.1

CONTACT Chukwujindu M. A. Iwegbue maxipriestley@yahoo.com; jindumax@yahoo.com Department of Chemistry,


Delta State University, P.M.B., 1, Abraka, Delta State, Nigeria.
Supplemental data for this article can be accessed online at https://doi.org/10.1080/10406638.2021.1934046.
ß 2021 Taylor & Francis Group, LLC
2 C. M. A. IWEGBUE ET AL.

Foodstuff constitutes a major channel for human exposure to PAHs besides occupational
exposure and smoking. The prevalence, concentrations and compositions of PAHs in human
foods are controlled by the physiological and ecological characteristics of the products, environ-
mental contamination, and the type of thermal treatment involved during the industrial process
of food production or home preparation. Culinary methods that involve heat, such as baking,
barbecuing, boiling, frying, grilling, smoking, and roasting, can alter the PAH compositions and/
or introduce significant amounts of PAHs into human foods.2–8
In 2008, the European Food Safety Authority (EFSA) Contam Panel suggested that using benzo(a)-
pyrene (BaP) concentrations alone as an index of occurrence and toxicity of carcinogenic PAHs in
foods could be misleading, and recommended the use of a system of sums of PAH concentrations,
namely, PAH2 (benzo(a)pyrene [BaP] þ chrysene [Chry]), PAH4 (PAH2 þ benzo(a)anthracene [BaA]
þ benzo(b)fluoranthene [BbF]) or PAH8 (PAH4 þ benzo(k)fluoranthene [BkF] þ dibenz(a,h)anthra-
cene [DahA] þ indeno(1,2,3-cd)pyrene [IndP] þ benzo(g,h,i)perylene [BghiP]), as better indices for
PAH toxicity effects. However, the EFSA noted that the system of eight PAHs (PAH8) provides no
more added value than the system of four PAHs (PAH4) since the additional four PAHs are not com-
monly found in foods.9
A number of studies have demonstrated that PAH concentrations in different types of vege-
table oils are related to the methods applied in the processing of the oil and/or, to a lesser extent,
to environmental contamination.10–16 In canned fish products, such as mackerel, sardines and
tuna, oil and tomato-based sauces play the role of a preservative. Usually, the oil and tomato-
based sauces in canned fish are consumed alongside the fish products. Notably, very few studies
on the concentrations of PAHs in oil-based sauces of canned foods have been reported. Moret et
al. found as much as 248.2 mg kg1 of PAHs in oil sauces from canned food.10 Herein, we sought
to evaluate the PAH concentrations in oil and tomato-based sauces from some brands of canned
fish products commonly consumed in Nigeria. This study follows-on from our previous report
on the concentrations of PAHs in canned fish.8 Data from such an investigation are needed for
estimating dietary intakes and likely risks of exposure to PAHs through consumption of oil and
tomato-based sauces from canned fish products. In addition, the results enable consumers to
make knowledgeable decisions on food choices and consumption patterns, so as to minimize the
risks arising from exposure to PAHs in oil and tomato sauces from canned fish products.

Materials and methods


Sample collection
In this study, 31 brands of canned fish products (comprising of 10 brands of mackerel, 15 brands
of sardine, and 6 brands of tuna) were purchased from different retail outlets in Abraka, Asaba,
Benin City, Lagos, Onitsha and Warri in Nigeria. The selection of the brands was based on avail-
ability, market popularity, and to reflect those consumed by diverse income groups. For each
brand, 5–7 samples were collected, and the oil/tomato sauces from the same brand were drained
into a clean beaker and homogenized to form a composite sample of the brand. A subsample was
taken from the composite sample and processed for chromatographic analysis. Information
regarding the oil and sauce types, and the country of origin, for these canned fish products are
provided in Supplementary Material Table S1.

Reagents and chemicals


A commercial mixed standard solution containing 2000 mg mL1 of each of the 16 US EPA prior-
ity PAHs was diluted with acetone to different concentrations for instrument calibration
(AccuStandard Inc., New Haven, CT). A standard solution containing 1000 mg mL1 each of six
POLYCYCLIC AROMATIC COMPOUNDS 3

isotopically labeled PAHs, namely, d8-NaP, d10-Ace, d10-Phen, d12-Chry, d12-DahA, and d12-pery-
lene, was obtained from Cambridge Isotope Laboratories Inc., Tewksbury, MA, USA. Acetone,
acetonitrile (HPLC-grade), anhydrous sodium sulfate, and silica gel were products of Merck,
Darmstadt, Germany, and alumina was from BDH Chemicals, Poole, UK.

PAH extraction and clean-up


A mass of 2.5 g of the oil/sauce sample was diluted with 10 mL of a 60:40 (v/v) acetonitrile-acet-
one mixture, agitated for 5 min in a mechanical shaker and, subsequently, subjected to ultrasoni-
cation for 20 min and centrifuged at 4000 rpm for 5 min. The upper layer was decanted into a
clean beaker and the mouth sealed with aluminum foil. The process was repeated three times
with fresh aliquots of the acetonitrile-acetone mixture. The extracts were pooled and concentrated
to 2 mL by rotatory evaporation. The extract was subjected to purification in a multi-layer col-
umn consisting of neutral silica gel (4 g, 5% deactivated), neutral alumina (2.0 g, 6% deactivated)
and anhydrous sodium sulfate (5.0 g) loaded from bottom to top. The PAHs were eluted from
the column with 50 mL of the acetonitrile-acetone mixture, and concentrated under a slow flow-
ing stream of nitrogen gas to 2 mL.

GC-MS analysis
The PAH concentrations in the oils and tomato sauces were determined with an Agilent 6890 gas
chromatograph coupled to an Agilent 5773c mass selective detector (Agilent, Palo Alto, CA,
USA). A DB-5 fused silica capillary column (30 m length, 0.25 mm internal diameter and 0.25 mm
film thickness) was used to effect the separation. The mobile phase (carrier gas) used was helium
gas flowing at a velocity of 1.0 mL min1. An injection volume of 1 mL of the sample was injected
into the GC-MS via a pulsed splitless mode. The GC oven temperature was initially fixed at 50  C
for 1 min, then increased to 180  C at 8  C min1 and from 180 to 230  C at 5  C min1, and
finally increased from 230 to 300  C at 3  C min1 and held for 5 min at 300  C.

Quality assurance/control
The integrity of the analytical procedure was cross-checked by the recovery of surrogate PAHs
and a spiked matrix recovery method. In the case of the spiked matrix recovery method, known
PAH concentrations were added to selected samples that had been previously analyzed. The ana-
lysis of the spiked sample matrix was carried out following all the steps undertaken during the
analysis of samples. The average recoveries of the surrogate PAHs ranged from 73.6 to 98.1%,
while recoveries of 82.6 to 102% were achieved for the spiked matrix method. An external cali-
bration method was used for the quantification of PAH concentrations in the samples. The cali-
bration lines yielded r2 values of 0.9992 to 0.9998, and were obtained for the 16 PAHs as plots of
peak areas of the PAHs versus their known concentrations. The limits of detection (LODs) and
quantification (LOQs) for the PAHs ranged from 0.3 to 1.7 mg kg1 and 1.0 to 5.0 mg kg1
respectively.

Statistical analysis
Analysis of variance (ANOVA) was used to determine if the differences in the concentrations of
PAHs within a product type were significant (p < 0.05), while the Tukey test was used for com-
parison of the mean concentrations of PAHs between oils/sauces of different fish types. All statis-
tical calculations were carried out with SPSS version 19.0 software.
4 C. M. A. IWEGBUE ET AL.

Risk assessment
Estimation of dietary intake
In this study, the concentrations of BaP, and the EFSA indicators such as PAH2, PAH4 and PAH8,
were used to estimate the dietary intakes of PAHs arising from the ingestion of the oil and tomato
sauces from canned fish. The estimated daily intake (EDI) was determined from Equation (1):
 MI  CM
EDI ng kg 1 bw day1 ¼ (1)
BWA
where MI (g) represents the mass of the oil/tomato sauce from the canned fish consumed per
day which in this case was 9.0 g per day. The daily intake was derived from the assumption that
two canned fish products are consumed per week, and the average mass of the oil/sauce in the
can was divided by the number of days. BWA (kg) repesents the average body weight of an adult.
In this study, the average body weight of an adult was taken to be 60 kg. CM denotes the concen-
tration of BaP/EFSA indicators.

Margin of exposure. The margin of exposure (MOE) associated with consumption of the oil and
tomato sauce from the canned fish products was determined by using Equation (2):
MOE ¼ BMDL10
EDI  106 (2)
where BMDL10 signifies the lower bound of a 95% confidence interval for the benchmark dose
(BMD) that produced a 10% tumor incidence.9 EDI denotes the estimated dietary intake of PAHs
obtained from the levels of BaP and EFSA indicators measured in the samples. A MOE value <
10 000 signifies deleterious health effects; while a MOE value > 10 000 depicts no deleterious
health effects to humans.9 The BMDL10 values for BaP, PAH2, PAH4 and PAH8 are 0.07, 0.17,
0.34 and 0.49 mg kg1 bw day1 respectively.9

Hazard index and incremental life cancer risk. The hazard index (HI) is a measure of the non-
carcinogenic risk and is estimated by using Equations (3)-(4). The incremental lifetime cancer
risk (ILCR) relating to the consumption of oils and tomato sauces from canned fish products was
estimated from the USEPA model equation (Equation (5)).17
CDI ingnc
HI ¼ (3)
RfD
C  IngR  EF  ED
CDI ingnc ¼  CF (4)
BW  ATnc
C  IngR  EF  ED  CSF
ILCR ¼  CF (5)
BW  ATca
where CDIing-nc denotes the chronic daily intake arising from ingestion of PAH-contaminated oils
and sauces from canned fish products, C is the concentration of PAHs in the oils and tomato
sauces, and CF is a conversion factor (1  106). The ingestion rate (IngR) is the amount of oil
or sauce consumed per day (9.0 g day1), EF represents the exposure frequency (once daily for
350 days year1), ED represents the exposure duration in years (6 years and 30 years for children
and adults respectively), BW represents the average body weight (15 kg for children and 60 kg for
adults), ATnc represents the averaging time for non-carcinogens in days (2190 and 10950 days for
children and adults respectively), CF is the conversion factor (1  106 kg mg1) and RfD is the
oral reference dose for PAH compounds. The RfD values for PAHs are 0.02, 0.06, 0.06, 0.04,
0.04, 0.3, 0.04 and 0.03 for Nap, Acy, Ace, Flu, Phen, Ant, Flt and Pyr respectively.18 CSF (mg
kg1 day1) represents the oral slope factor. The CSF values for the seven carcinogenic PAHs,
namely, BaA, BaA, Chr, BbF, BkF, BaP, and IndP are 0.73, 0.0073, 0.73, 0.073, 7.3, 0.73, and 7.3
POLYCYCLIC AROMATIC COMPOUNDS 5

respectively,17 and ATca represents the averaging time for carcinogens in days (2190 and
19893 days for children and adults respectively). In this study, we adopted the average life expect-
ancy of 54.5 years for a Nigerian.19

Results and discussion


PAH concentrations and compositions in oil and tomato sauces from canned fish products
The concentrations of the 16 PAHs measured in tomato sauces and oils from canned fish are pre-
sented in Table 1. The concentrations of R16 PAHs varied from 101 to 698 mg kg1 for tomato
sauces from canned mackerel, 168 to 733 mg kg1 for oil-based sauces from canned sardines, and
204 to 459 mg kg1 for oil-based sauces from canned tuna. The concentrations and compositions
of PAHs in the tomato sauces and oils from canned fish showed significant variations (p < 0.05)
(Figure 1). The concentrations of PAHs in the tomato sauces and oils were higher than those pre-
viously reported for the fish components in these samples.8 The differences between the PAH
concentrations and compositions of the oils/sauces and fish components of these products can be
related to the oils used, canning temperatures, and interplay between the endogenous levels of
PAHs in the oils and ingredients of the tomato sauces and preferential desorption of PAHs from
the fish into the oil matrix during the canning processes, which is linked to the lipophilic nature
of PAHs. The PAH concentrations in the oil sauces from canned sardines were significantly
higher (p < 0.05) than those of the tomato sauces and oils from canned mackerel and tuna
respectively. Despite the differences in the number of samples, congeners and oil types studied,
the PAH concentrations in the oils and tomato sauces from these brands of canned fish are com-
parable to those found in vegetable oils in Nigeria16 and China,12 but were higher than those
reported for different varieties of vegetable oils and oil sauces in canned fish from Bangladesh,
Brazil and some European countries.10,11,13–15,20,21 The individual PAH concentrations and those
of total PAHs in the oils and tomato sauces from these canned fish products exceeded their
respective limits of 2.0 mg kg1and 25 mg kg1 prescribed by the German Society for Fat
Science.22 The levels of BaP, PAH2, PAH4 and PAH8 in the oil and tomato sauces varied from
5.5 to 116 mg kg1, not detected (nd) to 300 mg kg1, nd to 426 mg kg1 and nd to 636 mg kg1
respectively. The sample MS-1 had the highest loads of BaP, PAH2, PAH4 and PAH8 than the
other samples (Supplementary Material Table S2 ).
The permissible limits of BaP and PAH4 in edible oils and fats for human consumption as
specified by the European Union regulation (EU) No. 835/2011 are 2 mg kg1 and 10 mg kg1,
respectively.23 In addition, the European Commission regulation No. 1327/2014 specified the per-
missible limits of BaP and PAH4 in smoked fish and fishery products as 5.0 mg kg1 and 30.0 mg
kg1 respectively.24 The BaP concentrations in 39% of the samples exceeded the permissible levels
for BaP in oil and fishery products, while the PAH4 concentrations in all samples exceeded the
permissible limits for PAH4 in oils and fishery products except for samples MS-8, MS-9 and TS-
1 (Supplementary Material Table S2).
The levels of the seven carcinogenic PAHs (PAH7C) in the oils and tomato sauces ranged from
nd to 609, 65.4 to 996 and nd to 269 mg kg1 for tomato sauces from canned mackerel, and oils
from canned sardines and tuna respectively. The oil sauces from canned sardines contained
higher concentrations of PAH7C than the tomato sauces and oils from canned mackerel and tuna
respectively.
The compositions of the PAHs in the oils and tomato sauces from these brands of canned fish
showed dominance of 4–6 ring PAH homologues over 2-ring PAHs (Figure 1). The two-ring
PAH NaP was not detected in these samples except for one brand of canned sardines (SS-14).
The prevalence of 3-ring PAHs in these oils and tomato sauces varied from 30 to 50%, 13 to 53%
and 17 to 67% for tomato sauces from canned mackerel, oils from canned sardines, and oils from
6

Table 1. PAH concentrations (mg kg1) in oils and tomato sauces from canned fish.
Tomato sauce from canned mackerels Oil sauce from canned sardines Oil sauce from canned tuna
Mean StD Median Min Max Skew Mean StD Median Min Max Skew Mean StD Median Min Max Skew
NaP ND ND ND ND ND ND 112 0.0 112 112 112 0.0 ND ND ND ND ND ND
C. M. A. IWEGBUE ET AL.

Acy 83 71.6 43.6 23.9 166 0.57 42.3 21 44.9 10 63.5 1 111 31.3 111 88.6 133 0.0
Ace 41.6 15.7 34.1 31.1 59.6 1.66 121 158 47.5 24.9 399 2.1 26.8 0.0 26.8 26.8 26.8 0.0
Flu 42.3 26.2 48.6 13.5 64.7 1.02 30.8 13.3 30.1 10 50.1 0.1 28.4 0.0 28.4 28.4 28.4 0.0
Phen 31.8 13 24.3 24.2 46.8 1.73 38.6 4.2 38.6 35.6 41.6 0.0 36.5 10.5 36.2 24.5 49.2 0.2
Ant 27.1 0.0 27.1 27.1 27.1 0.0 57.5 95 11.7 6.7 200 2.0 29.6 7.2 29.6 24.5 34.7 0.0
Flt 68.8 51.8 53.8 24.6 143 1.48 44.1 42 33.3 9.6 127 2.0 115 160 35.7 10.2 300 1.7
Pyr 41.1 19.7 35.5 25.4 68.2 1.19 75.9 64.4 59.8 7.0 200 0.9 78.7 32.6 87.5 32.9 119 0.4
BaA 30.4 9.5 30.9 20 39.6 0.15 54.3 46.9 41.7 5.5 157 1.2 29.2 20.5 27.5 9.7 50.5 0.4
Chry 42.4 21.8 28.1 26.3 75 1.06 46.5 77.4 30.7 6.2 300 3.4 110 116 110 27.8 191 0.0
BbF 80.5 60.9 53 31.7 197 1.34 41.4 21.2 32.8 11.4 85.3 0.8 23.3 14.3 27.5 7.4 35.1 1.2
BkF 38.2 11.2 35.1 28.1 60 1.92 100 94.9 58.7 24 315 1.3 45.7 13.5 41.3 34.9 60.8 1.3
BaP 53.3 44.8 43.3 10.3 116 1.25 22.4 13.8 25.1 5.5 41.9 0.1 47.5 38.9 25.5 24.6 92.4 1.7
IndP 35.1 0.0 35.1 35.1 35.1 0.0 27.7 30 18 5.6 69.2 1.2 ND ND ND ND ND ND
DahA 92.5 61.8 104 25.7 148 0.83 17.1 10 17 7.2 27.3 0.0 ND ND ND ND ND ND
BghiP 34.2 13.3 29.6 24.6 57.6 2.0 32.6 15 35.3 11.5 52.6 0.2 24 0.0 24 24 24 0.0
TOTAL 305 191 239 101 698 1.12 393 167 387 168 733 0.4 317 97.0 278 204 459 0.7
2Rings ND ND ND ND ND ND 112 0.0 112 112 112 0.0 ND ND ND ND ND ND
3Rings 98.6 65.3 91.1 24.2 201 0.35 98.0 112 48.8 10 417 2.2 87 38.8 77.8 49 161 1.8
4Rings 110 81.0 72.0 43.1 265 1.42 140 130 73.3 30.7 425 1.4 209 122 183 60.7 362 0.2
5Rings 183 151 114 76.7 497 1.94 137 109 111 25.1 379 1.1 69.9 27 68.2 27.5 94.6 1.0
6Rings 41.3 18.5 32.0 24.6 64.7 0.6 34.2 28.8 31.3 5.6 82.9 0.8 24 0.0 24 24 24 0.0
7C 165 183 129 ND 609 1.75 310 294 224 65.4 996 8.1 109 91.9 93.5 0.0 269 1.0
PAH2 42.5 55.4 27.9 ND 191 2.53 56 74 35.9 6.2 300 3.1 90.4 72.7 72.9 24.6 191 1.2
PAH4 111 128 79.3 ND 426 1.86 122 81.4 87.5 25.3 354 1.8 104 63.3 92.4 53.3 208 1.5
PAH8 182 191 157 ND 636 1.6 231 130 218 90 519 0.8 136 81.3 116 55 269 1.4
Acenaphthylene (Acy), Acenaphthene (Ace), Fluorene (Flu), Phenanthrene (Phen), Anthracene (Ant), Fluoranthene (Flt), Pyrene (Pyr), Benzo(a)anthracene (BaA), Chrysene (Chry),
Benzo(b)fluoranthene (BbF), Benzo(k)fluoranthene (BkF), Benzo(a)pyrene (BaP), Indeno(1,2,3-cd)pyrene (IndP), Dibenzo(a,h)anthracene (DahA) and Benzo(ghi)perylene (BghiP),
Carcinogenic (C).
POLYCYCLIC AROMATIC COMPOUNDS 7

Figure 1. PAH profiles of (a) tomato sauces from canned mackerel, (b) oils from canned sardines, and (c) oils from canned tuna.

tuna respectively. In this study, the most frequently detected 3-ring PAHs were Acy, Flu and
Phen in the sauces from canned mackerel, sardines and tuna respectively. The low detection of 2-
and 3-ring PAHs in the oils and tomato sauces may be related to the fact that these compounds
8 C. M. A. IWEGBUE ET AL.

Table 2. BaPTEQ and BaPMEQ concentrations (mg kg1) of PAHs in oils and tomato sauces from canned fish.
Sauce BaA Chry BbF BkF BaP IndP DahA BaPTEQ BaA Chry BbF BkF BaP IndP DahA BaPMEQ
Tomato Mean 1.21 0.02 5.63 0.23 21.3 0.35 27.8 56.5 1.00 0.36 14.08 2.52 21.3 1.09 8.05 48.4
sauces from StD 1.66 0.03 6.31 0.21 37.8 1.11 53.3 93.8 1.36 0.45 15.78 2.36 37.8 3.44 15.5 67.0
canned Median 0.00 0.01 3.49 0.30 0.00 0.00 0.00 14.6 0.00 0.22 8.73 3.32 0.00 0.00 0.00 26.5
mackerel Min ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
Max 3.96 0.08 19.7 0.60 116 3.51 148 288 3.25 1.28 49.3 6.60 116 10.9 42.8 217
Skew 0.85 1.08 1.37 0.16 2.11 3.16 1.85 2.11 0.85 1.08 1.37 0.16 2.11 3.16 1.85 2.10

Oils from Mean 3.62 0.04 3.31 0.87 12.0 0.74 4.57 25.1 2.97 0.69 8.27 9.57 12.0 2.29 1.32 37.1
canned StD 4.60 0.07 2.54 0.95 15.2 1.88 9.11 19.1 3.77 1.25 6.36 10.4 15.16 5.83 2.64 25.4
sardines Median 2.47 0.02 3.06 0.40 5.50 0.00 0.00 19.0 2.03 0.41 7.65 4.38 5.50 0.00 0.00 35.2
Min ND ND ND ND ND ND ND 2.83 ND ND ND ND ND ND ND 5.79
Max 15.7 0.30 8.53 3.15 41.9 6.92 27.3 63.1 12.9 5.10 21.3 34.7 41.9 21.5 7.92 93.7
Skew 1.54 3.58 0.46 1.37 0.95 3.02 1.99 0.68 1.54 3.58 0.46 1.37 0.95 3.02 1.99 0.73

Oils from Mean 1.46 0.04 1.17 0.23 23.8 0.00 0.00 26.6 1.20 0.62 2.92 2.51 23.8 0.00 0.00 31.0
canned StD 2.06 0.08 1.57 0.26 35.8 0.00 0.00 35.0 1.69 1.30 3.92 2.91 35.8 0.00 0.00 33.6
tuna Median 0.49 0.00 0.37 0.17 12.3 0.00 0.00 15.7 0.40 0.00 0.93 1.92 12.3 0.00 0.00 21.5
Min ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND ND
Max 5.05 0.19 3.51 0.61 92.4 0.00 0.00 92.4 4.14 3.25 8.78 6.69 92.4 0.00 0.00 92.4
Skew 1.34 2.34 0.94 0.44 1.85 0.00 0.00 1.70 1.34 2.34 0.94 0.44 1.85 0.00 0.00 1.47

are preferentially associated with the gaseous phase. Detection of 4- to 6-ring PAHs in these sam-
ples ranged from 30 to 70%, 26 to 87% and 17 to 50% for tomato sauces from canned mackerel,
oils from canned sardines, and oils from canned tuna respectively. In the tomato sauces from
canned mackerel, Flt, DahA and IndP were the dominant 4-, 5- and 6-ring PAHs respectively,
whereas Pyr, BbF and BghiP were the respective prominent 4-, 5- and 6-ring PAHs in oil sauces
from canned sardine samples. In the case of oil sauces from canned tuna, Pyr, BkF and BghiP
were the respective prominent 4-, 5- and 6-ring compounds.

Risk assessment of PAHs in tomato sauces and oils from canned fish
Carcinogenic and mutagenic potency
The BaPTEQ and BaPMEQ values for PAHs in oils and tomato sauces from canned fish are shown
in Table 2. The BaPTEQ values varied from nd to 288 mg kg1 (mean 56.5 mg kg1) for tomato
sauces from canned mackerel, from 2.83 to 63.1 mg kg1 (mean 25.1 mg kg1) for oils from
canned sardines, and nd to 92.4 mg kg1 (mean 26.6 mg kg1) for oils from canned tuna. The
BaPMEQ values for PAHs in tomato sauces from canned mackerel ranged from nd to 217 mg kg1
(mean 48.4 mg kg1), while those for oil sauces from canned sardines and tuna were 5.79 to
93.7 mg kg1 (mean 37.1 mg kg1) and nd-92.4 (mean 31.0 mg kg1) respectively. The BaPTEQ and
BaPMEQ values for the tomato sauces were higher than those of oil sauces from canned sardines
and tuna. For the tomato sauces, samples MS-1 and MS-5 had higher BaPTEQ and BaPMEQ values
than the other samples (Supplementary Material Table S3). The BaPTEQ values of PAHs in the oil
and tomato sauces from canned sardines and mackerel were greatly influenced by the concentra-
tions of DahA and BaP, while those of oils from canned tuna were greatly influenced by the con-
centrations of BaP and BaA. The BaPMEQ values of PAHs in the tomato and oil sauces from
canned mackerel and tuna were influenced by the contributions from BaP and BbF, while the
BaPMEQ of oils from canned sardines were influenced by the concentrations of BaP and BkF.

Daily intakes, margin of exposure, and non-cancer and cancer risks


Table 3 presents summarized information on the daily intakes of the indicators for PAHs, such
as BaP, PAH2, PAH4 and PAH8, while estimated daily intakes of PAH indicators for the
POLYCYCLIC AROMATIC COMPOUNDS 9

Table 3. Daily intakes of PAHs in oils and tomato sauces from canned fish.
Child Adult
BaP PAH2 PAH4 PAH8 BaP PAH2 PAH4 PAH8
Tomato sauces from Mean 29.5 58.9 154 253 6.82 13.6 35.5 58.3
canned mackerel StD 52.4 76.8 178 264 12.1 17.7 41.1 61.0
Median 0.00 38.7 110 218 0.00 8.93 25.4 50.4
Min 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Max 161 265 590 882 37.2 61.2 136 204
Skew 2.11 2.53 1.86 1.60 2.11 2.53 1.86 1.60

Oils from canned sardines Mean 16.6 72.5 169 321 3.83 16.7 38.9 74.1
StD 21.0 101 113 181 4.85 23.3 26.0 41.7
Median 7.63 49.4 121 302 1.76 11.4 28.0 69.7
Min 0.00 0.00 35.1 125 0.00 0.00 8.10 28.8
Max 58.1 416 491 720 13.4 96.0 113.4 166
Skew 0.95 3.14 1.78 0.85 0.95 3.14 1.78 0.85

Oils from canned tuna Mean 32.9 83.5 120 157 7.60 19.3 27.7 36.3
StD 49.6 101.4 98.1 127 11.5 23.4 22.6 29.3
Median 17.1 54.0 102 146 3.94 12.5 23.6 33.8
Min 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Max 128 265 289 373 29.6 61.2 66.7 86.1
Skew 1.85 1.38 0.94 0.84 1.85 1.38 0.94 0.84

Table 4. Margin of exposure values for children and adults arising from consumption of oils and tomato sauces from canned
fish contaminated with PAHs.
Child Adult
Sauce type Sample BaP PAH2 PAH4 PAH8 BaP PAH2 PAH4 PAH8
Tomato sauces from MS-1 4341 6409 5762 5556 18809 27771 24971 24076
canned mackerel MS-2 0 46615 93229 134359 0 201996 403992 582224
MS-3 0 22331 11897 17145 0 96767 51553 74296
MS-4 11632 28248 30998 20641 50403 122408 134324 89442
MS-5 11712 28445 25514 10869 50754 123260 110562 47101
MS-6 49010 119025 55223 34883 212379 515777 239302 151160
MS-7 0 43629 16047 16598 0 189057 69535 71923
MS-8 0 0 0 0 0 0 0 0
MS-9 0 0 0 0 0 0 0 0
MS-10 0 44259 30881 24608 0 191787 133816 106633
Oils from canned sardines SS-1 19267 18547 22109 18530 83492 80371 95807 80296
SS-2 18491 15479 16771 9316 80128 67077 72674 40370
SS-3 0 4087 6920 6805 0 17708 29989 29487
SS-4 0 38674 30011 33087 0 167587 130049 143375
SS-5 91783 91490 33496 32810 397727 396455 145150 142177
SS-6 0 33866 28745 12143 0 146754 124560 52620
SS-7 13319 19742 16794 13744 57718 85548 72774 59559
SS-8 12048 21395 12484 11571 52208 92714 54099 50139
SS-9 54870 57288 41209 25313 237772 248248 178571 109688
SS-10 66422 161311 38735 8513 287829 699013 167852 36889
SS-11 21122 22454 28022 15768 91527 97299 121429 68329
SS-12 0 92876 17963 25888 0 402462 77839 112179
SS-13 0 34437 38252 39263 0 149228 165757 170139
SS-14 0 197736 12652 16224 0 856855 54825 70305
SS-15 0 0 96914 38874 0 0 419960 168454
Oils from canned tuna TS-1 0 0 0 0 0 0 0 0
TS-2 5463 13268 26536 30358 23674 57495 114989 131551
TS-3 0 0 44580 64248 0 0 193182 278409
TS-4 20521 49836 22250 24353 88923 215955 96416 105531
TS-5 19796 23001 46002 37354 85784 99672 199343 161866
TS-6 0 6412 11771 13131 0 27785 51008 56903
10

Table 5. Hazard index values for children and adults arising from consumption of oils and tomato sauces from canned fish contaminated with PAHs.
Child Adult

NaP Acy Ace Flu Phen Ant Flt Pyr HI NaP Acy Ace Flu Phen Ant Flt Pyr HI
MS-1 0.00 0.00 0.00 0.00 0.00 0.00 2.07  10-3 0.00 2.07 3 10-3 0.00 0.00 0.00 0.00 0.00 0.00 4.77  10-4 0.00 4.77 3 10-4
C. M. A. IWEGBUE ET AL.

MS-2 0.00 0.00 1.32  10-3 0.00 0.00 0.00 1.51  10-3 0.00 2.83 3 10-3 0.00 0.00 3.05  10-4 0.00 0.00 0.00 3.48  10-4 0.00 6.53 3 10-4
-3
MS-3 0.00 3.67  10-3 0.00 0.00 0.00 0.00 4.75  10-3 1.23  10-3 9.65 3 10 0.00 8.47  10-4 0.00 0.00 0.00 0.00 1.10  10-3 2.84  10-4 2.23 3 10-3
-4
MS-4 0.00 5.70  10-4 0.00 0.00 0.00 0.00 0.00 0.00 5.70 3 10 0.00 1.31  10-4 0.00 0.00 0.00 0.00 0.00 0.00 1.31 3 10-4
-4
MS-5 0.00 0.00 0.00 0.00 8.04  10-4 0.00 0.00 0.00 8.04 3 10 0.00 0.00 0.00 0.00 1.86  10-4 0.00 0.00 0.00 1.86 3 10-4
MS-6 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MS-7 0.00 9.66  10-4 0.00 0.00 1.56  10-3 1.20  10-4 8.18  10-4 1.13  10-3 4.59 3 10-3 0.00 2.23  10-4 0.00 0.00 3.59  10-4 2.77  10-5 1.89  10-4 2.60  10-4 1.06 3 10-3
MS-8 0.00 5.30  10-4 7.56  10-4 1.62  10-3 8.08  10-4 0.00 0.00 1.91  10-3 5.62 3 10-3 0.00 1.22  10-4 1.74  10-4 3.73  10-4 1.86  10-4 0.00 0.00 4.41  10-4 1.30 3 10-3
-3
MS-9 0.00 3.46  10-3 6.89  10-4 4.49  10-4 0.00 0.00 0.00 3.02  10-3 7.62 3 10 0.00 7.99  10-4 1.59  10-4 1.04  10-4 0.00 0.00 0.00 6.98  10-4 1.76 3 10-3
-3
MS-10 0.00 0.00 0.00 2.15  10-3 0.00 0.00 0.00 0.00 2.15 3 10 0.00 0.00 0.00 4.96  10-4 0.00 0.00 0.00 0.00 4.96 3 10-4
-3
SS-1 0.00 0.00 8.83  10-3 5.95  10-4 0.00 0.00 0.00 0.00 9.43 3 10 0.00 0.00 2.04  10-3 1.37  10-4 0.00 0.00 0.00 0.00 2.18 3 10-3
-3
SS-2 0.00 0.00 2.19  10-3 9.51  10-4 0.00 0.00 0.00 0.00 3.14 3 10 0.00 0.00 5.05  10-4 2.19  10-4 0.00 0.00 0.00 0.00 7.24 3 10-4
-3
SS-3 0.00 0.00 7.36  10-4 1.29  10-3 1.38  10-3 0.00 0.00 4.43  10-3 7.84 3 10 0.00 0.00 1.70  10-4 2.98  10-4 3.19  10-4 0.00 0.00 1.02  10-3 1.81 3 10-3
SS-4 0.00 0.00 0.00 1.67  10-3 0.00 0.00 4.21  10-3 8.86  10-3 1.47 3 10-2 0.00 0.00 0.00 3.84  10-4 0.00 0.00 9.71  10-4 2.05  10-3 3.40 3 10-3
SS-5 0.00 0.00 0.00 3.32  10-4 0.00 5.85  10-5 3.19  10-4 1.21  10-3 1.92 3 10-3 0.00 0.00 0.00 7.67  10-5 0.00 1.35  10-5 7.36  10-5 2.80  10-4 4.44 3 10-4
-3
SS-6 0.00 0.00 0.00 0.00 1.18  10-3 0.00 1.39  10-3 6.43  10-3 9.00 3 10 0.00 0.00 0.00 0.00 2.73  10-4 0.00 3.21  10-4 1.48  10-3 2.08 3 10-3
-3
SS-7 0.00 0.00 1.05  10-3 0.00 0.00 0.00 0.00 0.00 1.05 3 10 0.00 0.00 2.43  10-4 0.00 0.00 0.00 0.00 0.00 2.43 3 10-4
-3
SS-8 0.00 1.26  10-3 0.00 0.00 0.00 0.00 0.00 0.00 1.26 3 10 0.00 2.92  10-4 0.00 0.00 0.00 0.00 0.00 0.00 2.92 3 10-4
-3
SS-9 0.00 0.00 0.00 8.41  10-4 0.00 4.52  10-5 6.65  10-4 4.74  10-4 2.03 3 10 0.00 0.00 0.00 1.94  10-4 0.00 1.04  10-5 1.53  10-4 1.09  10-4 4.67 3 10-4
-3
SS-10 0.00 0.00 0.00 1.05  10-3 0.00 2.97  10-5 0.00 2.14  10-3 3.21 3 10 0.00 0.00 0.00 2.42  10-4 0.00 6.85  10-6 0.00 4.93  10-4 7.42 3 10-4
-4
SS-11 0.00 2.22  10-4 0.00 0.00 0.00 0.00 0.00 0.00 2.22 3 10 0.00 5.11  10-5 0.00 0.00 0.00 0.00 0.00 0.00 5.11 3 10-5
SS-12 0.00 0.00 0.00 0.00 0.00 0.00 1.13  10-3 3.75  10-3 4.88 3 10-3 0.00 0.00 0.00 0.00 0.00 0.00 2.60  10-4 8.65  10-4 1.13 3 10-3
SS-13 0.00 9.95  10-4 0.00 0.00 0.00 0.00 0.00 2.65  10-3 3.65 3 10-3 0.00 2.30  10-4 0.00 0.00 0.00 0.00 0.00 6.12  10-4 8.41 3 10-4
-2
SS-14 7.43  10-3 7.96  10-4 5.52  10-4 1.45  10-3 0.00 0.00 0.00 3.10  10-4 1.05 3 10 1.71  10-3 1.84  10-4 1.27  10-4 3.35  10-4 0.00 0.00 0.00 7.16  10-5 2.43 3 10-3
-3
SS-15 0.00 1.41  10-3 0.00 0.00 0.00 8.86  10-4 1.08  10-3 0.00 3.38 3 10 0.00 3.25  10-4 0.00 0.00 0.00 2.05  10-4 2.50  10-4 0.00 7.79 3 10-4
TS-1 0.00 0.00 0.00 0.00 8.14  10-4 1.09  10-4 9.97  10-3 2.77  10-3 1.37 3 10-2 0.00 0.00 0.00 0.00 1.88  10-4 2.51  10-5 2.30  10-3 6.38  10-4 3.15 3 10-3
-3
TS-2 0.00 2.94  10-3 0.00 9.44  10-4 0.00 0.00 0.00 0.00 3.89 3 10 0.00 6.79  10-4 0.00 2.18  10-4 0.00 0.00 0.00 0.00 8.97 3 10-4
-3
TS-3 0.00 0.00 0.00 0.00 1.09  10-3 1.54  10-4 1.19  10-3 5.29  10-3 7.72 3 10 0.00 0.00 0.00 0.00 2.52  10-4 3.55  10-5 2.74  10-4 1.22  10-3 1.78 3 10-3
-3
TS-4 0.00 0.00 0.00 0.00 1.31  10-3 0.00 0.00 3.88  10-3 5.19 3 10 0.00 0.00 0.00 0.00 3.03  10-4 0.00 0.00 8.95  10-4 1.20 3 10-3
TS-5 0.00 0.00 5.94  10-4 0.00 1.64  10-3 0.00 0.00 1.46  10-3 3.69 3 10-3 0.00 0.00 1.37  10-4 0.00 3.77  10-4 0.00 0.00 3.37  10-4 8.51 3 10-4
TS-6 0.00 1.96  10-3 0.00 0.00 0.00 0.00 3.39  10-4 4.04  10-3 6.34 3 10-3 0.00 4.53  10-4 0.00 0.00 0.00 0.00 7.82  10-5 9.32  10-4 1.46 3 10-3
Table 6. Total cancer risk values for children and adults arising from consumption of oils and tomato sauces from canned fish contaminated with PAHs.
Child Adult
BaA Chry BbF BkF BaP IndP DahA Total Cancer Risk BaA Chry BbF BkF BaP IndP DahA Total Cancer Risk
-5 -7 -4 -6 -3 -3 -3
MS-1 3.60  10 7.28  10 1.91  10 3.46  10 1.13  10 0.00 1.43  10 2.79 3 10 4.53  10-6 9.16  10-8 2.41  10-5 4.35  10-7 1.42  10-4 0.00 1.80  10-4 3.51 3 10-4
MS-2 0.00 2.55  10-7 0.00 0.00 0.00 0.00 0.00 2.55 3 10-7 0.00 3.21  10-8 0.00 0.00 0.00 0.00 0.00 3.21 3 10-8
MS-3 3.84  10-5 5.33  10-7 1.08  10-4 0.00 0.00 0.00 0.00 1.47 3 10-4 4.84  10-6 6.71  10-8 1.36  10-5 0.00 0.00 0.00 0.00 1.85 3 10-5
MS-4 0.00 0.00 3.47  10-5 3.35  10-6 4.21  10-4 0.00 0.00 4.59 3 10-4 0.00 0.00 4.36  10-6 4.22  10-7 5.30  10-5 0.00 0.00 5.78 3 10-5
MS-5 0.00 0.00 5.14  10-5 5.82  10-6 4.18  10-4 3.41  10-5 1.01  10-3 1.52 3 10-3 0.00 0.00 6.48  10-6 7.33  10-7 5.27  10-5 4.29  10-6 1.27  10-4 1.92 3 10-4
MS-6 0.00 0.00 3.31  10-5 3.14  10-6 1.00  10-4 0.00 0.00 1.36 3 10-4 0.00 0.00 4.17  10-6 3.95  10-7 1.26  10-5 0.00 0.00 1.71 3 10-5
MS-7 2.40  10-5 2.73  10-7 9.71  10-5 2.73  10-6 0.00 0.00 0.00 1.24 3 10-4 3.02  10-6 3.43  10-8 1.22  10-5 3.43  10-7 0.00 0.00 0.00 1.56 3 10-5
MS-8 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MS-9 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
MS-10 1.94  10-5 2.69  10-7 3.08  10-5 3.74  10-6 0.00 0.00 2.49  10-4 3.04 3 10-4 2.44  10-6 3.38  10-8 3.87  10-6 4.70  10-7 0.00 0.00 3.14  10-5 3.82 3 10-5
SS-1 3.24  10-5 3.87  10-7 1.11  10-5 7.75  10-6 2.54  10-4 0.00 0.00 3.06 3 10-4 4.08  10-6 4.88  10-8 1.39  10-6 9.75  10-7 3.20  10-5 0.00 0.00 3.85 3 10-5
SS-2 0.00 5.04  10-7 6.50  10-5 2.26  10-5 2.65  10-4 0.00 0.00 3.53 3 10-4 0.00 6.34  10-8 8.19  10-6 2.85  10-6 3.34  10-5 0.00 0.00 4.45 3 10-5
SS-3 2.40  10-5 2.91  10-6 2.87  10-5 1.34  10-5 0.00 0.00 2.65  10-4 3.34 3 10-4 3.02  10-6 3.67  10-7 3.62  10-6 1.68  10-6 0.00 0.00 3.34  10-5 4.20 3 10-5
SS-4 4.85  10-5 3.08  10-7 0.00 2.44  10-6 0.00 0.00 0.00 5.13 3 10-5 6.11  10-6 3.87  10-8 0.00 3.07  10-7 0.00 0.00 0.00 6.45 3 10-6
SS-5 0.00 7.67  10-8 5.80  10-5 0.00 5.34  10-5 0.00 6.99  10-5 1.81 3 10-4 0.00 9.65  10-9 7.31  10-6 0.00 6.72  10-6 0.00 8.80  10-6 2.28 3 10-5
SS-6 8.15  10-6 3.51  10-7 3.95  10-5 1.94  10-5 0.00 5.53  10-6 0.00 7.30 3 10-5 1.03  10-6 4.42  10-8 4.97  10-6 2.44  10-6 0.00 6.96  10-7 0.00 9.18 3 10-6
SS-7 8.14  10-5 2.35  10-7 0.00 1.02  10-5 3.68  10-4 5.44  10-6 0.00 4.65 3 10-4 1.03  10-5 2.96  10-8 0.00 1.29  10-6 4.63  10-5 6.84  10-7 0.00 5.86 3 10-5
SS-8 5.22  10-5 1.49  10-7 8.28  10-5 3.86  10-6 4.07  10-4 6.72  10-5 0.00 6.13 3 10-4 6.57  10-6 1.88  10-8 1.04  10-5 4.86  10-7 5.12  10-5 8.45  10-6 0.00 7.71 3 10-5
SS-9 5.34  10-6 1.18  10-7 3.16  10-5 5.70  10-6 8.93  10-5 0.00 9.61  10-5 2.28 3 10-4 6.72  10-7 1.49  10-8 3.98  10-6 7.17  10-7 1.12  10-5 0.00 1.21  10-5 2.87 3 10-5
SS-10 0.00 0.00 5.41  10-5 3.06  10-5 7.38  10-5 0.00 0.00 1.58 3 10-4 0.00 0.00 6.81  10-6 3.85  10-6 9.29  10-6 0.00 0.00 1.99 3 10-5
SS-11 0.00 2.98  10-7 3.19  10-5 2.87  10-6 2.32  10-4 2.94  10-5 2.34  10-4 5.30 3 10-4 0.00 3.75  10-8 4.02  10-6 3.62  10-7 2.92  10-5 3.70  10-6 2.94  10-5 6.68 3 10-5
SS-12 9.49  10-5 1.28  10-7 2.48  10-5 0.00 0.00 0.00 0.00 1.20 3 10-4 1.19  10-5 1.61  10-8 3.12  10-6 0.00 0.00 0.00 0.00 1.51 3 10-5
SS-13 2.77  10-5 3.46  10-7 0.00 2.51  10-6 0.00 0.00 0.00 3.05 3 10-5 3.48  10-6 4.35  10-8 0.00 3.16  10-7 0.00 0.00 0.00 3.84 3 10-6
SS-14 1.52  10-4 6.02  10-8 2.97  10-5 2.33  10-6 0.00 0.00 0.00 1.84 3 10-4 1.92  10-5 7.58  10-9 3.74  10-6 2.93  10-7 0.00 0.00 0.00 2.32 3 10-5
SS-15 0.00 0.00 2.46  10-5 2.94  10-6 0.00 0.00 0.00 2.75 3 10-5 0.00 0.00 3.09  10-6 3.70  10-7 0.00 0.00 0.00 3.46 3 10-6
TS-1 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
TS-2 0.00 0.00 0.00 0.00 8.97  10-4 0.00 0.00 8.97 3 10-4 0.00 0.00 0.00 0.00 1.13  10-4 0.00 0.00 1.13 3 10-4
TS-3 2.67  10-5 0.00 2.67  10-5 0.00 0.00 0.00 0.00 5.34 3 10-5 3.36  10-6 0.00 3.36  10-6 0.00 0.00 0.00 0.00 6.72 3 10-6
TS-4 4.90  10-5 0.00 3.41  10-5 3.39  10-6 2.39  10-4 0.00 0.00 3.25 3 10-4 6.17  10-6 0.00 4.29  10-6 4.26  10-7 3.01  10-5 0.00 0.00 4.09 3 10-5
TS-5 0.00 2.70  10-7 0.00 4.01  10-6 2.48  10-4 0.00 0.00 2.52 3 10-4 0.00 3.40  10-8 0.00 5.05  10-7 3.12  10-5 0.00 0.00 3.17 3 10-5
TS-6 9.42  10-6 1.86  10-6 7.18  10-6 5.90  10-6 0.00 0.00 0.00 2.44 3 10-5 1.19  10-6 2.34  10-7 9.04  10-7 7.43  10-7 0.00 0.00 0.00 3.07 3 10-6
POLYCYCLIC AROMATIC COMPOUNDS
11
12 C. M. A. IWEGBUE ET AL.

individual brands are presented in Supplementary Material Table S4. The median daily intakes of
PAH indicators for children consuming oils and tomato sauces from these canned fish varied
from nd to 161 ng BaP kg1 bw day1, nd to 416 ng kg1 bw day1 for PAH2, nd to 590 ng
kg1 bw day1 for PAH4, and from nd to 882 ng kg1 bw day1 for PAH8. In the case of
adults consuming these oils and sauces, the daily intake values for BaP, PAH2, PAH4 and
PAH8 were nd to 37.2, nd to 96.0, nd to 136 and nd to 204 ng kg1 bw day1 respectively. The
consumption of oils from canned sardines gave higher median intake values of PAH4 and
PAH8, while that of oils from canned tuna gave higher dietary median intakes of BaP and
PAH2. The dietary intakes of PAHs from ingestion of these oils and tomato sauces were higher
than those reported for consumption of canned fish,8 biscuits,25 honey26 fresh and smoked
fish27–29 and edible oils in Nigeria.16
The MOE values for BaP, PAH2, PAH and PAH8 arising from consumption of oils and
tomato sauces in these canned fish products by children and adults were generally higher than
10,000 except in the following cases in respect of children: samples MS-1, SS-3, BaP for TS-2, and
PAH2 for TS-6 (Table 4). The MOE values indicate there are no considerable adverse health
effects arising from consumption of oils and tomato sauces from these canned fish products.
The hazard index (HI) values for the exposure of adults and children to PAHs in oils and
tomato sauces of these canned fish products were less than 1 (Table 5), which signifies that there
is no considerable non-carcinogenic risk. However, the cancer risk values for the individual
PAHs arising from consumption of oils and tomato sauces from these canned fish products were
in the magnitude of 108 to 103 and 109 to 104 for children and adults respectively (Table 6).
The cancer risk values associated with BaP and BkF as individual compounds were in the magni-
tude of 103 to 107 (Table 6). This indicates that the concentrations of BaP and BbF are the
major determinants of the cancer risk values of PAHs in these oils and tomato sauces. A value of
106 (the probable risk of one person in a population of one million to suffer cancer or cancer-
related diseases) has been set as the acceptable cancer risk value. The total cancer risk, and those
of BaP and BbF as individual compounds, for adults and children ingesting these oils and tomato
sauces, were higher than the acceptable risk value of 106 which indicates that there is a consid-
erable risk relating to consumption of oils and tomato sauces from these canned fish types.

Conclusion
The study revealed that oils and tomato sauces of canned fish contained significant concentra-
tions of PAHs, and especially high molecular weight compounds. The levels of PAHs in these oil
and tomato sauce matrices followed the order: sardines > tuna > mackerel. The total cancer risk
values obtained in this study suggest that consumption of as much as 9.0 g of these oils and
tomato sauces per day could elicit a considerable cancer risk. The carcinogenic risk relating to
ingestion of oils and tomato sauces from these canned fish products was influenced by the con-
centrations of BaP and BbF. Bearing in mind the high concentrations of carcinogenic PAHs
found in these oils and sauces, it is therefore necessary for consumers to drain off the oils and
tomato sauces before consuming the fish components so as to reduce the risk of exposure
to PAHs.

Acknowledgements
BSM wishes to thank the National Research Foundation of South Africa for research support.

Disclosure statement
No potential conflict of interest was reported by the authors.
POLYCYCLIC AROMATIC COMPOUNDS 13

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