Changes in The Content of Heavy Met
Changes in The Content of Heavy Met
Changes in The Content of Heavy Met
Cieślik I., Migdał W., Topolska K., Gambuś F., Szczurowska K., Cieślik E. 2018.
Changes in the content of heavy metals (Pb, Cd, Hg, As, Ni, Cr) in freshwater
fish after processing – the consumer’s exposure.
J. Elem., 23(1): 247-259. DOI: 10.5601/jelem.2017.22.2.1436
ORIGINAL PAPER
2
Malopolska Centre of Food Monitoring
3
Department of Agricultural and Environmental Chemistry
University of Agriculture in Krakow
Abstract
Fish is a desirable component of a diet because of its high nutritive value and sensory qualities.
However, fish consumption is still low in many countries. The aim of this study was to assess
the content of Pb, Cd, Hg, As, Ni and Cr in the meat of freshwater fish and quantitative chan-
ges after processing (smoking or marinating). Moreover, the exposure of consumers to heavy
metals by eating a portion (100 g) of the examined products was estimated as well as the safe
amounts (comparing to the maximum limit - ML and as the Benchmark Dose Lover Confidence
limits – BMDL) of processed fish for two population groups. The research material consisted
of 3 species, i.e. common carp (Cyprinus carpio), rainbow trout (Oncorhynchus mykkis) and
northern pike (Esox lucius). The content of heavy metals (except for mercury) was determined
in samples of fresh as well as processed fish, using inductively coupled plasma optical emission
spectrometry (ICP-OES). In turn, for the determination of mercury, an AMA-254 Advanced
Mercury Analyzer was used. Nickel and chromium in all the samples were below limits of detec-
tion. The study revealed a relatively safe content (below MLs) of heavy metals in almost all fish
samples, except for the cadmium concentration in fresh and smoked common carp as well as in
marinated rainbow trout. The calculated intakes of these contaminants through consumption of
one portion of the examined fish products were all below BMDLs and Tolerable Weekly Intakes
(PTWI or TWI).
INTRODUCTION
Research material
The research material consisted of 3 fish species, farmed in the Carp
Valley (Zator, Malopolska, Poland), i.e. common carp (Cyprinus carpio) –
Carp of Zator, rainbow trout (Oncorhynchus mykkis), and northern pike
(Esox lucius). A total of 6 fish from each species were collected. The age of
common carp was 2 years, and its weight was 1.5-2.0 kg; the age of rainbow
trout was 0.5 years and its weight was 0.5-1.0 kg; the pike’s age was 3 years
and its weight was 2-3 kg. The specimens were killed, washed, gutted,
cleaned and divided into parts. The samples were stored at -80°C until ana-
lyzed. The fish were also used to prepare smoked (common carp, rainbow
trout, northern pike) and marinated (common carp, rainbow trout) products,
according to traditional recipes. Prior to smoking, the samples were cured in
spices and stored at 4-8°C for 12 hours. Next, they were subjected to warm
smoking (4-6 h, smoke from fruit tree wood and alder wood in the last stage).
In turn, the marinating process (vinegar and water in the ratio 1:3, sugar,
mustard seed, bay leaf, allspice and slices of vegetables) was preceded
by deep-frying in rapeseed oil (until golden brown). Fish smoking as well
as preparation of marinated products were described in detail previously
(Cieślik et al. 2017).
Chemical analyses
A total of 18 samples of fresh fish (3 species) and 15 samples of fish
products (smoked or marinated) were determined. The content of Pb, Cd, As,
Ni and Cr was determined by the spectrometric method according to internal
laboratory procedures. Prior to analysis, material was freeze-dried using an
Alpha 1-2 LD Plus freeze dryer (Martin Christ, Germany). The process was
carried out at a temp. of -40°C and pressure of 0.2 mbar until constant mass
was obtained. A freeze-dried sample in the amount of 0.5 g was added to 5
ml of nitric acid (65%, Suprapur, Merck, Germany) and 1 ml hydrochloric
(30% Suprapur, Merck, Germany). Wet mineralization was performed in a
microwave system Multiwave 3000 (Anton Paar, Graz, Austria) under
following conditions: power of 800 W, reaching time of 10 min, holding time
of 20 min, ventilation time of 15 min. Next, the heavy metal levels were
measured using a spectrometer ICP-OES 7300 DualView (Perkin Elmer,
USA), at the following wavelengths: Pb 220.353 nm, Cd 228.802 nm,
As 188.979 nm, Ni 231.604 nm and Cr 267.716 nm. The detection limits
were: Pb – 0.042 mg L-1, Cd – 0.0027 mg L-1, As – 86 µg L-1, Ni – 0.0105 µg L-1
and Cr – 0.0071 mg L-1. Quality of analyses was ensured by making a paral-
lel analysis of Certified Reference Material IAEA-407 (Fish Homogenate).
The recovery for the applied method was: Pb – 104.59%, Cd – 94.71%,
As – 98.55%, Ni – 94.56% and Cr – 97.26%. The analysis of Hg was per-
250
Calculations
The results were compared with the current limit content of heavy me-
tals in fish and fish products, included in Commission Regulation (EC) No
629/2008, of 2 July 2008 amending Regulation (EC) No 1881/2006 setting
maximum levels for certain contaminants in foodstuff (European Commu-
nities 2008).
Additionally, the content of examined heavy metals was compared with:
–– Provisional Tolerable Weekly Intake (PTWI) of 25 µg kg-1 b.w./week for
lead, 7 µg kg-1 b.w./week for cadmium and 1.6 µg kg-1 b.w./week
for total mercury;
–– Tolerable Weekly Intake (TWI) of 2,5 µg kg-1 b.w. for cadmium;
–– Benchmark Dose Lower Confidence Limit (BMDL) for lead:
33 BMDL01 for children (neurotoxicity) – 0.50 mg kg-1 b.w./day;
33 BMDL10 for adults (nephrotoxicity) – 0.63 mg kg-1 b.w./day;
33 BMDL01 for adults (cardiovascular disorders) – 1.50 mg kg-1 b.w./day;
–– Benchmark Dose Lower Confidence Limit BMDL for mercury:
33 BMDL0.5 for adults (imunotoxicity) – 0.01 µg kg-1 b.w./day;
33 BMDL10 for adults (nephrotoxicity) – 0.06 µg kg-1 b.w./day;
–– Benchmark Dose Lower Confidence Limit BMDL for arsenic:
33 BMDL0.5 for adults (carcinogenic) – 3.00 µg kg-1 b.w./day.
The calculations were performed for adults (assuming 70 kg b.w.) and
children (assuming 35 kg b.w.) (Staszowska et al. 2013).
Fig. 1. The content of Pb (a) and Cd (b) in fish and fish products (mg kg-1) in comparison
to the Maximum Levels (ML): MLPb – 0.300 (mg kg-1), MLCd – 0.050 (mg kg-1); A, B, C – mean
values followed by the same letter are not significantly different (a = 0.05) – the differentiating
factor: fish species; a b c – mean values followed by the same letter are not significantly
different (a = 0.05) – the differentiating factor: technological process
fish metal uptake, i.e. age, size, feeding behavior and living environment (El
-Moselhy et al. 2014). The levels of Pb measured in fish products varied from
0.011 mg kg-1 (in smoked pike and trout) to 0.232 mg kg-1 (in marinated trout),
but no sample exceeded the maximum level (ML) of 0.30 mg kg-1 set by Com-
mission Regulation No 629/2008 (Figure 1a). A drop in the concentration of
heavy metals in samples after thermal treatment, attributed to the heat effect,
was observed in fish meat by Eboh et al. (2006) as well as Kobia et al. (2016).
Heavy metals could be converted to other compounds (Kobia et al. 2016).
The process of marinating led to a 5-fold increase in the Pb concentra-
tion in samples of rainbow trout (Figure 1a). This increase could be due to
252
Fig. 2. The content of Hg (a) and As (b) in fresh fish and fish products (mg kg-1):
A, B, C – mean values followed by the same letter are not significantly different (a = 0.05)
the differentiating factor: fish species; a b c – mean values followed by the same letter
are not significantly different (a = 0.05) – the differentiating factor: technological process
Human exposure
The threat posed by the examined heavy metals to consumer health was
analyzed based on their Provisional Tolerable Weekly Intakes. With regard
to PTWI (Table 1), one can conclude that in the presence of lead as a conta-
minant, an adult weighing 70 kg can consume 87.50 kg of smoked and mari-
nated common carp, 175.0 kg of smoked rainbow trout and 7.609 kg of mari-
nated rainbow trout, 175.0 kg of smoked northern pike, on a weekly basis.
In the case of cadmium, an adult can consume 7.000 kg of smoked common
carp and 12.25 kg of marinated common carp, 9.800 kg of smoked rainbow
Table 1
Amount of fish products (kg) containing the PTWIa (in male adult weighing 70 kg)
of the examined heavy metals
Northern
Common carp Rainbow trout
pike
Heavy metal
PTWIa PTWIb
marinated**
marinated**
smoked**
smoked**
fresh *
fresh *
fresh*
Pb 58.33 87.50 87.50 43.75 175.0 7.609 43.75 175.0 25.00 1750
Cd 4.083 7.000 12.25 12.25 9.800 6.125 16.33 16.33 7.000 490.0
Hg 1.867 2.240 11.20 5.600 2.240 5.600 5.600 1.600 1.600 112.0c
a
PTWI – Provisional Tolerable Weekly Intake, b in a male adult weighing 70 kg, c methylmer-
cury content – assumed that total mercury occurred as methylmercury
255
CONCLUSIONS
Fresh pike
Fresh pike
Fresh carp
Fresh carp
Fresh trout
Fresh trout
Smoked pike
Smoked pike
Smoked carp
Smoked carp
Smoked trout
Smoked trout
Sample
Sample
Marinated carp
Marinated carp
Marinated trout
Marinated trout
Mean dose of Hg in 100 g Mean dose of Pb in 100 g of meat
0.007
0.002
0.002
0.005
0.002
0.001
0.005
0.006
of meat (mg 100 g-1)
1.064
3.533
23.16
1.100
3.821
2.111
2.197
3.077
(µg 100 g-1)
BMDL0.5 for adult of body weight BDML01 for child of body weight
35 kg
0.700
70 kg (mg/adult/day)
17.50
(µg/child/day)
Intake of Hg from a portion of 100 Intake of Pb from a portion of 100 g
g of fish by child of body weight of fish by child of body weight 35 kg
1.000
0.286
0.286
0.714
0.286
0.143
0.714
0.856
6.080
20.19
132.3
6.286
21.83
12.06
12.56
17.58
35 kg (%BMDL0.5) (%BMDL01)
BMDL10 for adult of body weight BMDL10 for adult of body weight
4.200
70 kg (mg/adult/day) 70 kg
44.10
(µg/adult/day)
0.167
0.048
0.048
0.119
0.048
0.024
0.119
0.143
of fish by adult of body weight 70 kg
2.413
8.001
52.52
2.494
8.664
4.787
4.982
6.977
weight 35 kg (%BMDL10)
(%BMDL10)
12.60
17.14
3.461
23.29
30.46
1.490
3.474
2.483
of meat (µg 100 g-1) BMDL01 for adult (µg/person/day)
210.0
70 kg (µg/adult/day) of fish by adult of body weight 70 kg
BMDL values for lead, as the intake of Pb and Cd with one portion (100 g) of fish
1.013
3.365
22.06
1.048
3.639
2.010
2.092
2.930
(%BMDL01)
6.000
8.162
1.648
11.09
14.50
0.710
1.654
1.182
3.334
3.203
8.000
4.402
3.805
4.261
6.801
11.85
(almost 3-fold) and to a decrease in the As levels in all the samples except
for carp. It was stated that the examined processing methods caused a signi-
ficant increase in the concentrations of most metals compared to those of the
fresh samples. However, these technological practices also caused a decrease
in the concentrations of heavy metals in some fish types. This finding could
be attributed to the inter-play between the size of a processed fish, oil uptake,
water loss, and metal evaporation during the processing.
The calculated intakes of the examined heavy metals (consumption of
100 g fish portion) were below the BMDLs and Tolerable Weekly Intakes
(PTWI or TWI). Simultaneously, nickel and chromium were below limits of
detection in all samples.
The practical application of this study is to enhance the consumer’s
knowledge about heavy metals content in freshwater fish species after diffe-
rent ways of processing, both more popular like smoking and less common
like marinating.
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