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European Food Research and Technology

https://doi.org/10.1007/s00217-023-04343-5

ORIGINAL PAPER

Determination of the quality of smoked sea herring (Sardinella


maderensis) produced by three smoking processes practiced in Ivory
Coast
Mariam Cisse1,2 · Gaoussou Karamoko1 · Mohamed Cisse2 · Christine Chene3 · Romdhane Karoui1

Received: 23 April 2023 / Revised: 26 July 2023 / Accepted: 29 July 2023


© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023

Abstract
The aim of this study was to assess the impact of smoking processes applied in the Ivory Coast on the quality of sea herring
(Sardinella maderensis) collected from fishermen in the port of Abidjan. The samples were divided into three groups and
smoked using three smoking processes. The first two processes are based on including two artisanal smoking kilns with the
use of mangrove wood as combustible for one, and the rubber wood for the other. The third process is based on improved
kiln using FAO-Thiaroye processing Technique (FTT) with the combination of mangrove wood and coconut shells as com-
bustible. The results revealed that the highest values for pH (6.57 ± 0.09), moisture (54.14 g/100 g ± 1.61), peroxide value
(31.75 ± 1.89 meq ­O2/kg of fish), and total volatile basic nitrogen (37.03 ± 2.78 mg/100 g of fish) were found in samples made
with traditional smoking systems using rubberwood. The factorial discriminant analysis (FDA) applied to the concatenated
fluorescence spectra of aromatic amino acids and nucleic acids (AAA + NA) resulted in a 78.52% correct classification rate
of samples. Samples treated with rubberwood were the best discriminated, while those treated with mangrove wood and
mangrove wood combined with coconut shell remained confused due to the common used fuel: mangrove wood.

Keywords Smoking process · Fluorescence · Physico-chemical · Sea herring

Introduction Given the high level of fish consumption in the Ivory


Coast, preservation techniques are one of the most sustain-
Fish is one of the most widely consumed aquatic products able solutions for extending the shelf life of fish, which
in the world, with average global consumption estimated at remains a highly perishable product due to its composition.
17 kg of fish per capita per year [1]. Iceland, the Republic of However, fish preservation remains very difficult in develop-
Korea, Portugal, Norway, Japan, and Malaysia are the big- ing countries like Ivory Coast due to the lack of adequate
gest consumers of fish, consuming between 50 and 90 kg per infrastructure [5]. Among the preservation techniques,
capita per year [1]. In some African countries, such as Ivory smoking is the technique most used in Côte d’Ivoire [3].
Coast, fish is the most sought-after food in many households This process brings new sensory and textural characteristics
[2]. It occupies an important place in the Ivorian diet, with to fish [6] and also produces antimicrobial substances, such
an average per capita consumption of 15 to 16 kg/year/per- as phenols and formaldehyde [7].
son [3], and the most popular fish on the market are Horse Smoking is a technique that involves impregnating
Mackerel and Sardinella [4]. foodstuffs with the components of smoke to give them
a specific, highly sought-after taste and odor obtained
during the combustion of wood [8]. In Ivory Coast, sev-
* Romdhane Karoui
eral species of smoked fish are consumed such as Sar-
romdhane.karoui@univ-artois.fr
dinella maderensis that was reported as the raw mate-
1
Univ. Artois, Univ. Lille, Univ. Littoral Côte d’Opale, Univ. rial most commonly used for smoking (60–65 g/100 g)
Picardie Jules Verne, Univ. de Liège, INRAE, Junia, UMR-T (60–65 g/100 g) [9]. Ivoirian smoked fish sector’s actors
1158, BioEcoAgro, 62300 Lens, France use kilns, ranging from traditional to improved kilns
2
Univ. Péléforo Gon Coulibaly, Korhogo, Ivory Coast [10]. The former process kilns are made from a circular
3
Adrianor, Rue Jacquart, 62217 Tilloy‑les‑Mofflaines, France metal sheet and a parallelepiped-shaped oven. The latter

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remains, that is the most widely used in Abidjan and its the quality of smoked herring (Sardinella maderensis) by
around [11]. The circular sheet-metal kiln is used mainly assessing trace metal elements. In fact, the authors depicted
in inland towns outside Abidjan, while in some villages, that the technique used to smoke herring significantly
its rather traditional round mud kilns are used. However, increase cadmium and lead levels, and decreased mercury
the use of these traditional kilns with limited capacity is amounts.
confronted with: (i) heat and smoke losses, (ii) excessive To our best knowledge, to date, no studies were carried
fuel consumption, (ii) carbonization of products, and (iv) out on the characterization of smoked sea herring using
sanitary quality of fish. Face all identified shortcomings, physico-chemical and fluorescence techniques in Ivory
reflections have been conducted to make improvements Coast. Consequently, the main objective of the present study
to the practices of fish processors where the majority was to assess the effect of the smoking process on the qual-
of them are women. This is how a proven fish smoking ity of sea herring (Sardinella maderensis) through the use
technology called FAO-Thiaroye Processing Technique of targeted and untargeted techniques (physico-chemical,
(FTT) is that originated. This technology was developed colorimetry, and fluorescence spectroscopy).
by Food and Agriculture Organization (FAO) and the
National Training Centre for Fisheries and Aquaculture
Technicians (CNFTPA) in Senegal [12]. Since 2008, it has
been used in several African countries, in particular Ivory Materials and methods
Coast and to date, it has been disseminated to Asian and
Pacific countries. The FTT-Thiaroye kilns include Altona, Chemicals and reagents
Chorkor, Parpaing, and Thiaroye. The FTT-Thiaroye is a
smoking system based on an indirect smoking process. All chemical reagents used in this study were of analytical
The major innovation of this system was to separate the grade. Acetic acid, chloroform, saturated potassium iodide,
cooking phase from the smoking phase (exposure of the trichloroacetic acid, perchloric acid, and boric acid were pur-
product to smoke). Then, to prevent the grease from the chased from VWR International, while sodium thiosulfate
cooking product from falling onto the fuel and in turn was obtained from AppliCham.
generating deposits of tar particles on the product, and
finally to filter and lower the temperature of this smoke
[13]. The advantages of the FTT-Thiaroye oven are that it Preparation of smoked fish samples
improves product quality by reducing the polycyclic aro-
matic hydrocarbon content and giving the fish a uniform Forty-five samples of fresh herring (Sardinella maderensis)
color, it can operate in all weather conditions, and it helps ranging in weight and length from 150 to 229 g and 25 cm
to protect the environment by reducing wood consumption to 31 cm, respectively, were collected from fishermen in the
as a fuel [12]. port of Abidjan (Ivory Coast). The samples were then kept in
Fuel also plays a very important role in the smoking pro- polystyrene boxes filled with ice and transported to the vari-
cess, as the type of wood used. This latter has a major influ- ous smoking sites in less than 1 h. The forty-five (45) fresh
ence on the color, flavor, and smell of the smoked fish [14]. sea herring were randomly divided into three batches of 15
Fuels are used in the form of sawdust, shavings, or logs. samples and smoked by three smoking processes, as shown
Each type of wood has its specific organoleptic characteristic in Fig. 1 (an improved smoking process using FAO-Thiaroye
[15]. The wood used should generally be semi-dry, since processing Technique with a combination of mangrove wood
hardwoods produce less soot than softwoods. Softwoods, and coconut husk (ISMWC); and two artisanal smoking pro-
painted or varnished woods, plywood, or other materials cesses from artisanal kilns-based, fueled by mangrove wood
composed of several kinds of wood should be avoided, as the (ASMW) and rubberwood (ASRW)). Before each smoking
combustion of the paint, colorants, varnish, and chemicals process, fish were washed and left on grills to drain all the
generates more toxic and carcinogenic substances than pure wash water for 15 min. Measurements of the temperature
wood [16]. Indeed, rubberwood, considered a carcinogenic for each oven were determined with a digital thermometer
wood, is the most commonly used wood for the traditional (Checktemp 1, Hanna Instruments), by inserting the probe
smoking process, while redwood or mangrove wood is more into the oven and into the heart of the fish during the smok-
commonly used for the improved smoking process [10, 17]. ing. The characteristics of the three smoking processes are
Fish smoking was the subject of several studies in the mentioned below:
Ivory Coast, including socio-health analyses of fish smok-
ing [18, 19], determination of polycyclic aromatic hydrocar- (i) Improved smoking process (ISMWC) (Fig. 1a): fish
bons [10, 20] and microbiological parameters [9, 11]. Money were smoked in FTT-Thiaroye kiln using a combina-
et al. [14] depicted the impact of the smoking technique on

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Fig. 1  Smoking process practiced in Ivory Coast. a Improved smoking process at FTT oven with mangrove wood and coconut shell; b traditional
smoking process with mangrove wood; c traditional smoking process with rubber wood

tion of mangrove wood and coconut husk as fuel at a Total volatile basic nitrogen (TVB-N) content,
temperature that varied from 65 to 90 °C for 4 h; expressed in mg TVB-N/100 g of fish, was determined
(ii) Artisanal smoking process (ASMW) (Fig. 1b): man- using the KjeldahlTM 8100 automatic analyzer (Foss,
grove wood was used as fuel and smoking tempera- France) according to the Regulation (EC) No. 2074/2005,
ture varied between 60 and 95 °C for 3 h; (2008). All the analyses were made in triplicate.
(iii) And artisanal smoking process (ASRW) (Fig. 1c)
where the temperature ranged from 60 to 95 °C for Colorimetric measurements
3 h and rubberwood is used as a fuel.
The color measurements were performed directly on sea
After the smoking process, fish samples were kept herring samples using CR-300 spectrocolorimeter (Kon-
at room temperature for 30 min and then packaged in ica Minolta Sensing Europe, Roissy Charles De Gaulle,
a cardboard box. The smoked fish samples were kept at France), following the system of CIE (1976) and accord-
4 °C and then transported in less than 24 h in polystyrene ing to the method described by Botosoa et al. [23]. L*
boxes with dry ice to the UMR-T BioEcoAgro INRAe describes lightness (L* = 0 for black; L* = 100 for white),
1158 laboratory (France) for various analyses. a* describes intensity in red (+ 60 = red; − 60 = green), b*
describes intensity in yellow (+ 60 = yellow; − 60 = blue).
All the analyses were made in triplicate.
Physico‑chemical analysis

The pH value was measured directly on the smoked sea Fluorescence measurements
herring sample using a digital pH meter (WTW pH 330i
Taschen-pH-Meter, WTW GmbH) [20]. The moisture Fluorescence measurements were performed using a Fluo-
content was determined by drying 10 g of sea herring romax-4 spectrofluorometer (Jobin Yvon, Horiba, NJ, USA)
flesh in an oven (Air Concept, FIRLABO, Emerainville, equipped with a thermostatically controlled cell placed in a
France) at 105 °C for 24 h [21]. front angle cell holder set at 60 °C to reduce reflected light
The peroxide value (PV) was determined by the pro- and a Haake A25 CA 200 temperature controller (Thermo
cedure developed by Guizani et al. [22]. The values were Scientific, France) to control the temperature during analy-
expressed as milliequivalents of peroxide oxygen per kg sis. The smoked fish were ground with a Retsch type (GM
­ 2/kg of fish). The thiobarbituric acid reac-
of fish (meq O 200) mill for 1 min at a speed of 3000 rpm, then 2–3 g of
tive substances (TBARS) value, expressed as mg malonal- fish were placed in a 10 mm quartz cell, and the spectra were
dehyde (MDA)/kg of fish), was evaluated according to the scanned at 20 °C. The emission spectra of aromatic amino
method of Karoui & Hassoun [20]. The absorbance was acids and nucleic acids (AAA + NA) (290–400 nm), trypto-
determined at 532 nm using a UV-2600 visible spectro- phan residues (305–450 nm), nicotinamide adenine dinucle-
photometer (Shimadzu, France). otide (NADH) (360–600 nm), and riboflavin (405–650 nm)
were acquired with an excitation wavelength set at 250,

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290, 340, and 380 nm, respectively. The excitation spectra 6.57 ± 0.09 and showed a significant difference (p < 0.05)
of vitamin A (250–390 nm) were recorded with the emission according to the smoking process. The highest pH value was
wavelength set at 410 nm. For each sample, three measure- observed for smoked fish produced with the artisanal smok-
ments were made. ing system using rubber wood as combustion (ASRW), while
the lowest pH value was obtained for smoked fish made with
Multidimensional data analysis the improved smoking system using mangrove wood and
coconut shell as fuel (ISMWC). It should be noted that the
To differentiate between the three smoking techniques, pH values obtained for the smoked fish in our study were: (i)
ANOVA was applied to the physico-chemical and colorimet- close to those observed by Adegunwa et al. [26] on smoked
ric data using Fisher’s method at a level of 5 g/100 g. The herring (Sardinella eba) where pH ranging between 5.92
fluorescence data were subjected to normalization by reduc- and 6.57 was obtained; and (ii) higher than those depicted
ing the area under each spectrum to a value of 1 [24]. Prin- by Osheba [27] who observed values in the 5.79–6.14 for
cipal component analysis (PCA) and factorial discriminant smoked sea herring. Generally, a lower pH value is preferred
analysis (FDA) were then applied to the normalized data to as it increases the shelf life and induces better organoleptic
study the difference between the smoked herring samples. characteristics of the product [28]. The change in the pH val-
Finally, the first 5 PCs of the PCA applied to each fluo- ues between the three smoking processes could be attributed
rophore (AAA + NA, tryptophan, NADH, riboflavin, and to the: (i) difference in the production amount of volatile
vitamin A) representing more than 99% of the total variance basic compounds, such as ammonia, trimethylamine, and
were combined into a single matrix, and the new table was total volatile nitrogen by fish spoilage bacteria [29]; and/or
analyzed by the FDA with leave-one-out cross-validation (ii) absorption of some organic acids and ­CO2 by the flesh
factorial analysis [25]. Statistical analyses were performed during the smoking process [30].
using Matlab and XLSTAT 2013 Software. The highest moisture content was found for the
smoked sea herring samples from ASRW with a value of
54.1 g/100 g, while the lowest one was noted for the smoked
Results and discussion sea herring from ASMW presenting a moisture content of
45.32 g/100 g. The moisture content of smoked sea her-
Physico‑chemical parameters of smoked sea herring ring varied from 49.35 to 54.14 g/100 g, lower than the
fresh herring which presented a level of moisture content of
The physico-chemical data are summarized in Table 1a. The 77.24 g/100 g This means that smoking reduced the mois-
pH value of smoked sea herring ranged from 6.28 ± 0.03 to ture content of herring between 27.89 and 23.1 g/100 g.

Table 1  (a) Physico-chemical and (b) color parameters of smoked sea herring samples (Sardinella maderensis) under different smoking condi-
tions
(a) Physico-chemical
Smoking process pH Moisture (g/100 g) Peroxide value (Meq TBARS (Mg MDA/ TVB-N
­O2/kg of fish) kg of fish) (Mg/100 g of
fish)

Improved system ISMWC 6.28 ± 0.03a 49.35 ± 0.65a 18.28 ± 0.63a 1.29 ± 0.27a 27.85 ± 1.72a
Artisanal system ASMW 6.45 ± 0.04b 45.32 ± 2.36b 21.65 ± 1.72b 2.51 ± 0.28a 20.04 ± 0.68b
Artisanal system ASRW 6.57 ± 0.09c 54.14 ± 1.61c 31.75 ± 1.89c 1.71 ± 0.65a 37.03 ± 2.78c
(b) Color parameters
Smoking process L* a* b* ΔE*

Improved system ISMWC 60.4 ± 0.04a 2.46 ± 0.01a 26.89 ± 0.01a 66.16 ± 0.03a
Artisanal system ASMW 62.02 ± 0.03b 1.69 ± 0.00b 21.20 ± 0.01b 65.56 ± 0.03b
Artisanal system ASRW 67.05 ± 0.01c 0.64 ± 0.01c 21.54 ± 0.01c 70.43 ± 0.01c

(a) Different lowercase letters (a, b, c) in column represent statistical differences between the different smoking systems ((ISMWC) improved
system at FTT oven with mangrove wood and coconut husk; (ASMW) artisanal system with mangrove wood, and (ASRW) artisanal system
with rubberwood) at the 5% level of significance according to Fisher’s test; TBARS thiobarbituric acid reactive substances, TVB-N total volatile
basic nitrogen. (b) L* corresponds to luminance from 0 (black) to 100 (white), a* corresponds to the intensity of red (positive values) and green
(negative values) and b* characterizes the intensity of blue (positive values) and yellow (negative values); ΔE* corresponds to the total color
difference

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Industrial specifications for smoked products generally rec- high level of oxidation of polyunsaturated fatty acids in fish
ommend a moisture content in flesh fish below 65 g/100 g muscle [34], since, according to Coulibaly et al. [10], rubber
according to Cardinal et al. [31]. Our values were in agree- wood is known to be highly toxic in terms of polycyclic aro-
ment with this observation and were close to those obtained matic hydrocarbons and is not very rich in polyphenols, thus
by Adegunwa et al. [26], Osheba [27], and Gassem [32], promoting rapid oxidation in ASRW-treated samples. On the
who, respectively, noted moisture content values ranging other hand, the lowest PV observed in ISMWC conditions
between 50.68 and 77.75 g/100 g, 52.71–60.91 g/100 g, and could be due to fat saturation by smoke constituents, which
44.8 to 53.46 g/100 g for the smoked sea herring (Sardinella have strong antioxidant properties [35]. It is well known that
eba), smoked herring, and fermented salted fish, respec- the chemical composition of smoke is variable depending
tively. The levels of moisture content in the present study on the temperature and the amount of air present during
are greater than those reported by Adegunwa et al. [26] who pyrolysis [36]. The association of mangrove wood and the
noted moisture contents varying from 7.16 to 10.71 g/100 g coconut shell used in improved artisanal smoking conditions
for Nigerian smoked catfish. Furthermore, the moisture [28] might increase the phenolic compounds in smoked sam-
content values of smoked sea herring samples showed a ples under ISMWC conditions, because the coconut shell
significant difference (p < 0.05) according to the smoking would contain 1518 mg/L of phenol. In addition to the fuels
process. The smoked sea herring from ISMWC exhibited an used, temperature plays an important role in lipid oxidation,
intermediate value of 49.35 g/100 g (± 0.65). The variation because, according to Ramanathan [37], the extent of lipid
in moisture content of smoked fish is caused by different oxidation of smoked fish increased after cooking. Indeed,
factors of smoking processes such as the smoking time and temperature probably disrupts the muscle membrane system,
the temperature. The combination of coconut shell and man- thereby exposing lipid components to oxygen and other reac-
grove wood for smoking causes a slow combustion of the tion catalysts such as iron [38]. The higher the temperature,
wood which would lead to the formation of a layer of burn the more the samples are exposed to lipid oxidation.
charcoal. According to Nithin et al. [28], this charcoal layer The TBARS index is widely used as an indicator of the
would facilitate efficient heat transfer explaining the lower freshness of meat and fish [39–41]. The TBARS value
moisture content in samples from the improved smoking ranged from 1.29 to 2.51 mg MDA/kg of fish for smoked
system. Furthermore, it is clear that traditional smoking does sea herring samples under different smoking conditions.
not reduce the amount of water in the fish, as the difference These values are within the acceptable limit according to
between improved and traditional kilns lies in the design of the Egyptian standards (2005), which depicted that TBARS
the kilns and the fuels used. As traditional kilns are made values of smoked fish should not exceed 4.5 mg MDA/kg
from a metal barrel, it allows air and smoke to escape during of fish. Our values are: (i) similar to those reported by Gok-
the smoking process, resulting in a large amount of water tepe et al. [41] and Osheba [27], who found 1.19–1.49 mg
in the fish. In addition to the design of the oven and the MDA/kg of fish for smoked catfish filets stored in air at 2
fuel used during smoking, we can also note a smoking time and 8 °C, and 0.51–1.85 mg MDA/kg for smoked herring
and temperature variability, as the temperature of traditional (Clupea harengus), respectively, and (ii) higher than those
kilns ranges from 60 to 95 °C for 3 h, against 60 to 90 °C for observed by Adegunwa et al. [26], who noted values ranging
4 h for improved. All these factors contribute to limiting the between 0.02 and 0.11 mg MDA/Kg of smoked herring fish
shelf life of fish from traditional kilns, due to the high-water (Sardinella eba). The low TBARS values could be attributed
content of the fish. to the antioxidant activity of phenols in the smoke absorbed
The PV is one of the indicators that determine the level by the fish during the smoking process and also depending
of lipid oxidation [22, 33]. The PV of sea herring smoked on the smoking method and temperature [42]. On the other
under different smoking conditions showed a maximum hand, the increase in the TBARS value could be attributed
value for ASRW (31.75 ± 1.89 meq O ­ 2/kg of fish), a mini- to the partial dehydration of the fish and the increased oxi-
mum value for ISMWC (18.28 ± 0.63 meq ­O2/kg of fish), dation of unsaturated fatty acids resulting from smoking at
and an intermediate value for ASMW (21.65 ± 1.72 meq relatively high temperatures (up to 70 °C) [43].
­O2/kg of fish). The PV of smoked fish using the ISMWC The TVB-N value is an important indicator of fish fresh-
process was in line with the conclusions of Majumdar et al. ness, which reflects the degree of protein and amine deg-
[33], who obtained values of 16.27, 16.31, and 19.12 meq radation [44]. A limit of acceptability of 25–30 mg TVB-
­O2/kg of fish, respectively, for Channa striatus, Glossogob- N/100 g fish was defined as the TVB-N level above which
ius giuris, and Wallago attu. The PV of smoked fish samples smoked fish is considered unfit for human consumption [45].
produced with ISMWC and ASMW conditions was within The TVB-N level of smoked sea herring samples produced
the acceptable limits of PV according to Jónsdóttir et al. under different smoking conditions ranged from 20.04 to
[34], as it is less than 20 meq O ­ 2/kg of fish. The increase 37.03 mg TVB-N/100 g of fish. Only smoked fish samples
in PV in ASRW-treated samples is thought to be due to the from ISMWC and ASMW conditions showed values within

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limit acceptability (27.85 and 20.04 mg TVB-N/100 g of parameters of fish samples were affected by the smoking
fish, respectively), indicating that these samples were suit- processes. Regarding the L* value (luminosity index),
able for human consumption. These results confirmed that the highest value was found for the samples from ASRW
those obtained with the PV and are in disagreement with the 67.05 ± 0.01, which could be explained by the denatura-
values obtained with the TBARS. The smoked sea herring tion and oxidation of the proteins as depicted by Karoui
samples from ASRW exhibited values above the accept- et al. [49] and Boughattas et al. [50] for fresh and frozen-
able limit (37.03 mg TVB-N/100 g of fish). Nevertheless, thawed sea bass (Dicentrarchus labrax) filets and sturgeon
our results were lower than those reported by Gassem [32], (Acipenser gueldenstaedtii) stored at 4 °C, respectively. In
who found TVB-N values varying of 32.20–131.82 mg addition, the a* and b* parameters exhibited the highest
TVB-N/100 g of fish for salted fermented fish. Accord- values for the samples smoked under ISMWC conditions,
ing to El-Sherif et al. [46], the increased TVB-N levels in respectively, of 2.46 ± 0.01 and 26.89 ± 0.01. This indicates
smoked samples are mainly caused by an autolytic process a movement in the color of the fish flesh tending toward red
that produces compounds from volatile amines. This could and yellow color. The ISMWC conditions allowed fish to
be attributed to the action of hydrolysis of proteins caused have a flesh color going toward red and yellow. It should
by enzymes for a long time and the lowering of heat tem- be noted that the improved system has a smoke generator
perature during smoking. The highest TVB-N values were unlike the traditional system where the fish is smoked in the
observed for smoked samples under ASRW conditions. This open, giving uneven coloring to the fish during the smoking
trend could be explained by the presence of an important process. These results are in agreement with those obtained
amount of polycyclic aromatic hydrocarbons in the rubber by Asamoah et al. [51], who obtained 60.56 ± 12.25 for L*;
wood [10]. Indeed, according to the findings of Stołyhwo 2.66 ± 2.49 for a*and 20.03 ± 0.95 for b* on smoked mack-
and Sikorski [47], traditional oven-smoked fish samples con- erel skin and muscle. However, our results are different from
tain high levels of BaP (50 µg/kg) compared to improved those obtained by Rybicka et al. [52], who reported values
oven-smoked fish samples. The increase in TVB-N values for smoked mackerel samples varying from 49.2 to 55.6 for
could also be explained by the fact that the traditional smok- L*, 1.6 to 3.3 for a*, and 17.0 to 20.0 for b*.
ing technique does not allow to reduce significantly the level To obtain more information on the evolution of color
of water in the final product allowing it to expose the product parameters between the fish samples under different smok-
to the proliferation of microorganisms. This could induce the ing conditions, the total color difference (ΔE) was deter-
formation of ammonia, dimethylamine, and trimethylamine mined. The highest value was observed for samples smoked
in fish [48]. under ASRW conditions (70.43 ± 0.01) and the lowest one
was noted for those produced under ASMW (65.56 ± 0.03)
Colorimetric parameters of smoked sea herring and ISMWC (66.16 ± 0.03) conditions. Our ΔE values
were different from those obtained by Birkeland & Bjerk-
Table 1b shows the color parameters for the studied smoked eng [53], where ΔE values of 4.5 ± 1.2 and 5.1 ± 1.1 were
sea herring. A significant difference at (p < 0.05) was noted observed for cold smoked Atlantic salmon filets kept at
between the smoked fish samples, indicating that the color 4 °C and 12 °C, respectively. Furthermore, according to

Fig. 2  a Similarity map of PCA determined by principal component ASMW (artisanal mangrove wood system) (circle), and ASRW (arti-
(PC1) and (PC2) of physico-chemical and colorimetric parameters of sanal rubberwood system) (triangle) conditions; b correlation chart of
smoked sea herring samples (Sardinella maderensis) under ISMWC variables
(improved system of mangrove Wood and Coconut shell) (square),

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Fig. 3  Normalized fluorescence emission spectra of a AAA + NA emission 410 nm) recorded on sea herring samples (Sardinella made-
(excitation 250 nm; emission 290–400 nm), b tryptophan residues rensis) samples under ISMWC (improved system at FTT oven using
(excitation 290 nm; emission 305–450 nm), c NADH (excitation mangrove wood and coconut shell) (hyphen dashed lines), ASMW
340 nm; emission 360–600 nm), d riboflavin (excitation 380 nm; (artisanal mangrove wood system) (doted lines), and ASRW (Artisa-
emission 405–650 nm), and e vitamin A (excitation 250–390 nm; nal rubberwood system) (thick line) conditions

Lerfall and Rotabakk. [54], the observed color differences Analyses of physico‑chemical and colorimetric
between the samples might explain how the smoke com- parameters using PCA
ponents reacted with the chemical compounds like fatty
acids in the muscle. The PCA similarity map and the correlation map performed
on the physico-chemical and colorimetric data are shown
in Fig. 2a and b, respectively. A clear discrimination was
observed between fish according to the smoking conditions

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and/or carbonyl compounds. This trend was confirmed by


the tryptophan emission spectra presented in Fig. 3b, which
showed a similar trend as AAA + NA spectra with a maxi-
mum fluorescence intensity at 376 nm. It appeared that the
tryptophan emission spectra were not also affected by the
smoking conditions.
The normalized NADH, riboflavin, and vitamin A spectra
acquired on smoked sea herring samples (Fig. 3c–e, respec-
tively) allowed a better clear differentiation between samples
as a function of the smoking conditions. The NADH spectra
acquired on ASRW samples showed maximum fluorescence
intensity at 475 nm, while those belonging to ASMW and
ISMWC exhibited a maximum fluorescence intensity at 474
Fig. 4  Discriminant analysis similarity determined by discriminant and 473 nm, respectively. Furthermore, the spectra of the
factor F1 and F2, FDA performed on the 25 concatenated PCs cor- samples from ASRW showed the highest fluorescence inten-
responding to the PCA performed on fluorescence spectra of sea her-
ring samples (Sardinella maderensis) under ISMWC (improved sys- sity compared to the spectra of the samples from the two
tem at FTT oven using mangrove wood and coconut shell) (square), other groups. The difference in the fluorescence intensity
ASMW (artisanal mangrove wood system) (circle), and ASRW (arti- between the investigated samples could be due to the pres-
sanal rubberwood system) (triangle) conditions ence of many different fluorescent compounds in the smoke.
Given the results obtained with smoked herring NADH
from the map defined by PC1 and PC2, representing 74.4% emission spectra, it could be concluded that the NADH
and 23.7% of the total variance, respectively (Fig. 2a). This could be more oxidized in ASRW condition, indicating that
map showed the presence of three groups. Indeed, according NADH spectra can be considered as a fingerprint to differ-
to the PC1, smoked samples from ASRW exhibited posi- entiate the smoked fish according to the smoking conditions.
tive score values, while those from ISMWC had negative For the riboflavin spectra (Fig. 3d), the maximum fluo-
score values. Regarding smoked samples from ISMW, they rescence intensity was located at 518 nm for ASRW, 513
presented negative score values according to the PC2 and and 512 for ISMWC and ASMW samples, respectively. The
were differentiated from the two other groups. Discrimina- maximum peaks could be attributed to the proto-porphyrin
tion based on the chemical composition of the combustibles IX. Furthermore, in the 400–500 nm region, β-carotene may
was highlighted according to the smoking conditions. undergo photo-degradation [56], which may influence the
To investigate the basis of this discrimination between the shape of the riboflavin spectra. According to Durek et al.
smoked sea herring samples according to their smoking con- [57], the storage process accelerates the development of
ditions, the correlation circle was studied (Fig. 2b). Accord- porphyrin-producing microorganisms and activates the
ing to the PC1, fish samples from ASRW were character- enzymes involved. The use of rubber wood as a fuel seems to
ized by higher values of moisture content, TVB-N, PV, pH, accelerate the growth of microorganisms in ASRW samples,
L*, and total difference of color, while those from ISMWC because according to Chabi et al. [48], traditional smok-
exhibited the higher values of b* and a*. The PC2 showed ing does not meet hygienic standards, hence the presence of
a higher value of TBARS for ISMW samples. porphyrin-producing microorganisms in rubberwood-treated
samples.
Evaluation of fluorescence measurements The spectra of vitamin A acquired on the smoked sea her-
of smoked sea herring fish ring samples under different smoking conditions showed two
dominant peaks located at 295 and 351 nm for all the inves-
Figure 3a shows the normalized AAA + NA emission spectra tigated samples (Fig. 3e). The highest fluorescence intensity
recorded on smoked sea herring under ISMWC, ASMW, of the first peak was observed for the ASRW samples and the
and ASRW conditions. It appears that the AAA + NA emis- highest fluorescence intensity of the second peak was noted
sion spectra of sea herring under different smoking con- for ASMW and ISMWC samples. This difference could be
ditions were similar. It should be noted that the shape of attributed to the different physical states of triglycerides in
AAA + NA spectra recorded after excitation at 250 nm fat globules, and/or the membrane interactions of fat glob-
depends on the content of proteins and nucleic acids, their ules with the protein network and/or lipid–lipid interactions
structures, and the interactions of proteins with other cel- as reported by Karoui et al. [58]. According to Rustad [59],
lular components [55]. The highest fluorescence intensity lipid oxidation products can interact with amino acids, pep-
was observed at 394 nm, which could be due to the presence tides, proteins, nucleic acids, deoxyribonucleic acid (DNA),
of phenolic compounds, polycyclic aromatic hydrocarbons, and phospholipids to form fluorescent products. All these

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Table 2  Classification table of Smoking process ASRW ASMW ISMWC Total Correct clas-
samples of smoked sea herring sification (%)
(Sardinella maderensis) under
different smoking conditions: AAA + NA
(ISMWC) improved system at
Improved system ISMWC 2 10 33 45 73.33
FTT oven, (ASMW) artisanal
system, and (ASRW) artisanal Artisanal system ASMW 5 29 11 45 64.44
system Artisanal system ASRW 44 1 0 45 97.78
Total 51 40 44 135 78.52
NADH
Improved system ISMWC 5 14 26 45 57.78
Artisanal system ASMW 8 19 18 45 42.22
Artisanal system ASRW 39 5 1 45 86.67
Total 52 38 45 135 62.22
Riboflavin
Improved system ISMWC 9 16 20 45 44.44
Artisanal system ASMW 4 24 17 45 53.33
Artisanal system ASRW 40 2 3 45 88.89
Total 53 42 40 135 62.22
Tryptophan
Improved system ISMWC 5 14 26 45 57.78
Artisanal system ASMW 5 24 16 45 53.33
Artisanal system ASRW 42 2 1 45 93.33
Total 52 40 43 135 68.15
Vitamin A
Improved system ISMWC 1 16 28 45 62.22
Artisanal system (ASMW) 7 26 12 45 57.78
Artisanal system ASRW 36 2 7 45 80.00
Total 44 44 47 135 66.67
Concatenation: AAA + NA, NADH, riboflavin, tryptophan, vitamin A
Improved system ISMWC 2 13 30 45 66.67
Artisanal system ASMW 2 30 13 45 66.67
Artisanal system ASRW 43 1 1 45 95.56
Total 47 44 44 135 76.30

AAA+NA aromatic amino acids and nucleic acids, NADH nicotinamide adenine dinucleotide, ISMWC
improved system at FTT oven using mangrove wood and coconut husk, ASMW artisanal system using man-
grove wood, ASRW artisanal system using rubberwood

factors could accelerate the oxidation of fish lipids, leading the smoked sea herring samples under different smoking
to an increase in PV, which is in agreement with the fluores- conditions. The similarity map of the PCA does not allow
cence spectra of vitamin A. to effectively discriminate between the investigated smoked
Due to the complexity of the samples, univariate analysis samples. The FDA was therefore applied to the first 5 PCs
could not differentiate between the samples studied. In this of: (i) each fluorophore, and (ii) 5 fluorophores using the
case, multivariate analyses will be carried out to obtain more concatenation approach.
information on the spectral data set. The best result of the FDA was obtained with AAA + NA
spectra with a correct classification rate of 78.52%. The
highest classification was obtained for the ASRW group,
Discrimination based on fluorescence spectra since 97.78% of the samples were correctly classified. The
on smoked sea herring under smoking conditions worst classification was noted for ASMW, since correct
classification varied from 42.22 to 64.44% for the 5 fluo-
To extract information from the spectral data sets, PCA was rophores. Samples from ASRW showed better classifica-
applied separately, to each fluorescence data recorded on tion compared to those from ISMW and ISMWC, with an

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overall correct classification of 97.78, 86.67, 88.89, 93.33,


and 80.00% for AAA + NA, NADH, riboflavin, tryptophan,
Funding This work has been carried out in the framework of the
and vitamin A, respectively. However, the worst classifica- IDEAL project, which is financed by the French State, and the French
tion was observed for the samples from ISMW for all fluo- Region of Hauts-de-France. The authors gratefully acknowledge the
rophores, except the riboflavin. ISMWC samples exhibited financial support from the Major Domain of Interest (DIM) “Eco-
the worst classification for the riboflavin spectra where only Energy Efficiency” of Artois University. Mrs. CISSE is grateful to the
Embassy of France in Ivory Coast, for the financial support during her
44.44% of correct classification was obtained. ISMW and stay at the University of Artois.
ISMWC samples presented some similarities due to the fact
both smoking conditions used the same combustibles, which Data availability The authors confirm that data will be made available
is mangrove wood. It should be concluded that the concat- upon request.
enation technique allowed to distinguish between smoked
sea herring samples as a function of smoking conditions. Declarations
The concatenated FDA similarity map, defined by DF1 Conflict of interest The authors have no conflicts of interest.
and DF2 representing 81.18 and 18.82% of the total vari-
ance, respectively, separated herring samples into two Compliance with ethics requirements This article does not contain
any studies with human or animal subjects.
groups (Fig. 4). Indeed, according to the DF1 (81.18% of
the total variance), the majority of the smoked samples from
the ISMW and ISMWC had positive scores, while the other
samples from the ASRW presented negative scores accord- References
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