1 s2.0 S096399692400156X Main
1 s2.0 S096399692400156X Main
1 s2.0 S096399692400156X Main
A R T I C L E I N F O A B S T R A C T
Keywords: This study aimed to explore the concentrations of Se and Hg in marine fish along the Gulf of Mannar (southeast
Seafood coast of India) and to assess related risks and risk-based consumption limits for children, pregnant women, and
Hg toxicity adults. Se concentrations in pelagic and benthic fish ranged from 0.278 to 0.470 mg/kg and 0.203 to 0.294 mg/
Se intake
kg, respectively, whereas Hg concentrations ranged from 0.028 to 0.106 mg/kg and 0.026 to 0.097 mg/kg,
Target hazard quotient
Risk–benefit analysis
respectively. Se and Hg contents in demersal fish (Nemipterus japonicus) were 0.282 and 0.039 mg/kg, respec
Consumption advisories tively. The lowest and highest Hg concentrations in pelagic fish were found in Scomberomorus commersoni and
Food Safety Euthynnus affinis whereas the lowest and highest Se concentrations in benthic fish were found in Scarus ghobban
and Siganus javus. Se concentrations in marine fishes were found in the following order:
pelagic > demersal > benthic whereas Hg concentrations were found in the following order:
pelagic > benthic > demersal. The presence of Se in fish was positively correlated with trophic level (TL) and size
whereas that of Hg was weakly correlated with TL and habitat and negatively correlated with size. Se risk–benefit
analysis, the AI/RDI (actual intake/recommended daily intake) ratio was > 100 % and the AI/UL (upper limit)
ratio was < 100 %, indicating that all fish have sufficient levels of Se to meet daily requirements without
exceeding the UL. Hg level was below the maximum residual limit (MRL) of 0.5 mg/kg for most fish but it was
1 mg/kg in E. affinis and Lethrinus lentjan. The target hazard quotient (THQ < 1) and hazard index (HI < 1) imply
that the consumption of fish poses no noncarcinogenic health risks. However, all examined fish had a mean Se/
Hg molar ratio > 1, indicating that human intake of fish was rather safe relative to Hg content. Health benefit
indexes (Se-HBV and HBVse) with high positive values in all fish supported the protective effect of Se against Hg
toxicity, suggesting the overall safety of fish consumption. The high Se/Hg ratio in fish could be attributed to the
replacement of Se bound to Hg, thereby suppressing Hg toxicity and maintaining normal selenoprotein synthesis.
This insight is useful for a better understanding of food safety analysis.
* Corresponding authors at: Department of Fish Quality Assurance and Management, Fisheries College and Research Institute, Tamil Nadu Dr. J. Jayalalithaa
Fisheries University, Tuticorin 628 008, Tamil Nadu, India.
E-mail addresses: [email protected], [email protected] (U. Arisekar), [email protected], [email protected] (R. Shalini).
https://doi.org/10.1016/j.foodres.2024.114086
Received 27 September 2023; Received in revised form 14 January 2024; Accepted 31 January 2024
Available online 2 February 2024
0963-9969/© 2024 Elsevier Ltd. All rights reserved.
U. Arisekar et al. Food Research International 180 (2024) 114086
150 years (Li et al., 2020, 2023). Hg travels vast distances and gets toxicity of the toxic elements (TEs) in organisms such as fish/shellfish
deposited from the atmosphere to remote locations, leading to wide and humans (Burger et al., 2013). Examining the Se/Hg molar ratio in
spread exposure to every organism, including animals at sea thereby different fish/shellfish is crucial owing to the protective effect of Se
directly influencing seafood (Azad et al., 2019). Natural and human- against Hg toxicity (Burger et al., 2013; Scheuhammer et al., 2015).
made sources contribute to Hg discharges into coastal and marine en Instead of only looking at the total Hg, it is advised to calculate the Se/
vironments (Haris et al., 2017). Hg in the aquatic environment is con Hg (or Hg/Se) molar ratio and the toxicity of Hg (Scheuhammer et al.,
verted into MeHg by sulfate-reducing bacteria (MeHg) (Barrouilhet 2015). Recently, the Se/Hg molar ratio and the Se health benefit value
et al., 2023) and makes them more toxic and bioavailable for organism (Se-HBV) have gained popularity as methods of evaluating Hg toxicity
accumulation (Hajeb et al., 2010; Reddy et al., 2023). Hg gets bio (Squadrone et al., 2015; Kaneko and Ralston, 2007; Olmedo et al.,
accumulated in fish tissue as methyl Hg over time after being ingested by 2013). Se-HBV was used to investigate the health benefits of Se and
the fish (Souza-Araujo et al., 2016). MeHg constitutes the predominant, the risks associated with Hg exposure through seafood consumption.
and often fatal, form of Hg (70–100 %) found in fish muscle across the The edible muscles of commercially available fish have been the primary
majority of species (Azad et al., 2019; Llull et al., 2017). focus of research (Burger and Gochfeld, 2012; Squadrone et al., 2015).
Both forms of Hg and MeHg in fish/food are high enough to have To highlight the potential protective advantages of Se against Hg
detrimental health consequences, especially for developing fetuses and poisoning, only a small number of research have systematically exam
children (UNEP/WHO, 2008). The risk of poor neurodevelopment in ined Hg and Se concentrations and their molar ratio in fish (Burger et al.,
offspring owing to fatal exposure to Hg has been linked to maternal 2013; Ralston et al., 2008). Determining the potential protective bene
consumption of fish during pregnancy. Pregnant women (PW) and fits of Se against Hg poisoning requires immediate examination of
young children (C) are more vulnerable to the health risks associated diverse fish tissues. There is still a lot of debate among scientists about
with Hg because of its ongoing biomagnification in higher trophic level how to weigh the benefits of nutrients against the risks of pollutants.
(TL) predatory fish (Burger et al., 2012; Hajeb et al., 2010). Selenium However, several clinical investigations have demonstrated that the
(Se), a trace element naturally occurring in the environment, holds health advantages of ingesting a range of seafood species in the advised
essential nutritional benefits and biological functions. It is produced by amounts exceed the health hazards connected with Hg.
various industrial activities such as mining (coal, hard rock, uranium, Many studies have focused on determining the concentrations of TEs
and phosphate), refineries (metal and oil), power generation (coalfired (As, Cd, Hg, and Pb) in fish/shellfish for human consumption in Tamil
power plants), sewages/wastewater (industry or corporation) and Nadu (Shalini et al., 2020, 2021a,b; Yogeshwaran et al., 2020; Kumar
agriculture (irrigation waters and selenium fortification) (Chapman et al., 2021; Adani et al., 2022; Arisekar et al., 2020, 2021,b, 2022a-c,
et al., 2010). However, a small amount of Se is present in the earth’s 2023; Akila et al., 2022; Ulaganathan et al., 2022a,b), India (Suresh
crust at an estimated amount of 0.05–0.5 mg/kg, with total selenium et al., 2015; Arulkumar et al., 2017; Shree et al., 2019; Pragnya et al.,
concentrations in rocks comprising 40 % of the total earth’s crust, 2021), and globally (Looi et al., 2016; Azad et al., 2019; Grgec et al.,
mainly in sandstone, quartzite, and limestone (Tan et al., 2018). Se is 2020; Younis et al., 2021; Kazemi et al., 2022). However, limited
available/released in the environment in the form of selenate (SeO2− 4 ) attention has been given to the investigation of TE (Se and Hg) in fish
and selenite (SeO2−3 ). Both selenium oxyanions are toxic to living sys and shellfish related to its feeding behavior and TL (Zhang et al., 2016;
tems, although SeO−3 is more toxic than SeO2− 4 (Tan et al., 2018). Se Javanshir Khoei, 2023). To the best of our knowledge, no studies have
enters the water by soil drainage, air deposition, and naturally enriched examined Se/Hg molar ratio, Se-HBVs, HBVse, and their related human
subsoils in Se. In the forms of selenate and sodium selenide, it can be health risk assessment (HHRA) in pelagic, demersal, and benthic fish in
found in surface waters, groundwater, and saltwater. Highly soluble and the Tamil Nadu region along the southeast coast of India (SECI). In-
mobile suspended particles such as organic methylated species readily depth mechanistic investigations are difficult due to the lack of under
absorb the selenite form (Ralston et al., 2016; Copat et al., 2014). A standing regarding the relationship between total Hg and Se in fish
portion of the Se in the food gets absorbed and converted into a physi tissues. Therefore, these monitoring studies are necessary to determine
ologically usable form. The chemical form of Se present in the meal the Hg contamination levels and identifying possible risks associated
significantly affects bioavailability. In comparison to inorganic Se, with ingesting pelagic, benthic, and demersal fish captured from the
organic Se molecules are more bioavailable (Yin et al., 2020; Wu et al., Gulf of Mannar (GoM; Tuticorin coast). Research of this nature is crucial
2023). Se is generally absorbed at a high rate (70–95 %), and regional because it might shed light on how marine fish can benefit from Se’s
variations for absorption in Se have been documented globally. There protective actions against Hg poisoning. Hence, the following are the
fore, only people living in places with low ambient Se levels would objectives of the current investigation: (i) to evaluate the concentration
benefit from Se supplements. Unfortunately, Se is hazardous at con of Hg and Se in pelagic and benthic fish; (ii) to study the correlation
centrations slightly higher than those needed for homeostasis. Higher Se between Hg and Se concentration in fish and their size and feeding
concentrations might cause genotoxicity and cytotoxicity (Ghorai et al., behavior; (iii) to ascertain the Se/Hg molar ratios, HBVse. and Se-HBVs
2022). value of fish; and (iv) to establish the HHRA of Hg and protective
Marine fish is a good source of Se, offering several biological func mechanisms of Se from fish consumption. Further, this study is under
tions, antioxidant properties, and protective mechanisms against taken with the hypothesis that the selenium concentration suppresses
pollutant toxicity and diseases (Jia et al., 2023). In contrast to Hg, the Hg toxicity, and examines the correlation of selenium and mercury
selenium may have both positive and negative effects: (1) it is a mineral concentration with the length-weight, trophic level, and habitat of the
that is necessary in trace amounts for proper growth and animal fish. This work additionally provides fish consumption advisories to the
development; (2) appropriate amounts can be stored in an animal consumers. The study aims to contribute to the understanding of the
without affecting homeostatic mechanisms; and (3) large doses pose interactions between mercury and selenium in fish from the Gulf of
risk. Se has been linked to processes that control cell division and Mannar, providing insights into the potential health risks and benefits
apoptosis. Glutathione peroxidases and thioredoxin reductases are associated with consuming different types of marine fish.
members of the Se enzymes with antioxidant and detoxifying properties
(Burger et al., 2013; Gerson et al., 2020). There are few significant 2. Materials and methods
differences between the dosages associated with Se insufficiency and
toxicity. Therefore, it is crucial to keep the proper balance of this 2.1. Fish collection and preparation
micronutrient in the diet.
A high binding affinity of the Se seems to contribute to the seques A total of 130 composite fish samples comprising 13 commercially
tration and reduced bioavailability of MeHg or Hg, hence reducing the important marine teleost including Indian anchovy (Stolephorus indicus;
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U. Arisekar et al. Food Research International 180 (2024) 114086
van Hasselt, 1823), Indian oil sardine (Sardinella longiceps; Valenciennes, limit of quantification (LOQ) included using a concentration of Se that
1847), pink-handle barracuda (Sphyraena jello; Cuvier, 1829), ribbonfish was comparable to 10 times the SD (standard deviation) of 10 solvent
(Trichiurus lepturus; Linnaeus, 1758), seerfish (Scomberomorus commer blanks. Conversely, the limit of detection (LOD) was established by
soni; Lacepède, 1800), little tuna (Euthynnus affinis; Cantor, 1849), em considering the concentration of Se that corresponded to 3 times the SD
peror bream (Lethrinus lentjan; Lacepède, 1802), rabbitfish (Siganus of 10 solvent blanks. Every analytical batch (10 samples/batch) used a
javus; Linnaeus, 1766), areolate grouper (Epinephelus areolatus; Forsskål, standard solution (10 ppb) as a quality control check. The concentra
1775), spot tail needlefish (Strongylura strongylura; van Hasselt, 1823), tions of Se and Hg were estimated in the sample based on a six-point
Indian mackerel (Rastrelliger kanagurta; Cuvier, 1816), Japanese calibration curve (0.1, 0.5, 1.0, 5.0, 10, and 25 µg/kg) (HC 16386194;
threadfin bream (Nemipterus japonicus; Bloch, 1791), and parrot fish Supelco ICP multi-elemental standard purchased from Merck Life Sci
(Scarus ghoban; Forsskål, 1775) were collected from the Tuticorin coast ence Pvt. Ltd., Germany). The results were expressed as mg/kg on a wet
along the GoM region (8.7945◦ N, 78.1584oE). Fish were sampled dur weight basis. ICP-MS (Thermofisher Scientific, Germany) in collision
ing the summer season (during the year 2022), which is a suitable/ cell mode was used to analyze Se and Hg concentrations in fish. After the
favorable condition for Hg methylation (Hines et al., 2012). Fish sam system was up and running, the sensitivity, stability, oxide, and double
ples were collected from the Tuticorin fish landing center and brought to charge resolution of the ICP-MS instrument were all optimized by
the laboratory under iced conditions within an hour. Immediately, fish adjusting the flow rate of the atomizing gas, the position of the ion lens,
were washed with tap water, subsequently in distilled water, and wiped and the shape of the rectangular tube in accordance with the standard
with tissue paper. Then, the length and weight of the fish were taken, tune solution. To detect TEs, the following settings were applied to the
and after dressing, the meat was separated, homogenized, and stored in ICP-MS instrument: The RF generator power and frequency were both
a ziplock cover and stored at − 20 ◦ C for further analysis. The TE analysis set to 1000 W and 27 MHz, respectively. The flow rates for the plasma,
was conducted within 48 h. Ten composite samples were made for each nebulizer, and auxiliary gases were 15, 0.9, and 0.8 L/min, respectively.
fish species. For smaller fish weighing below 150–200 g, each composite High-purity argon and helium gas (>99.997 %) were used for cooling/
sample comprised six fish whereas larger fish with an average weight plasma and carrier gases. The KED mode was used for the measure
greater than 200 g were represented by 3–4 fish per composite sample. ments, and each sample was measured three times. The integration
Table 1 shows the common and scientific names of the fish sampled and duration was 1000 ms.
their length (cm), weight (g), habitat, eating pattern, and major/pref The standard calibration recovery percentage (RC%) of the Se ranged
erable food species. from 81.3 to 107.2 % with a mean recovery of 88.3 ± 11.4 % and that of
Hg from 85.8 to 101.6 % with a mean recovery of 95.1 ± 5.7 %. The
2.2. Sample digestion, elemental analysis and quality control concentrations of the examined elements showed an average recovery
between 80 % and 120 %, with standard deviations of 20 %, which
The concentration of Hg and Se at extractable levels was determined complied with the recommendations of the European Commission (EC/
following the AOAC 2015. 01 method for TE analysis in food using ICP- SANTE/2017) (EC, 2017, 2019). Yttrium (10 ppb) was used as an in
MS as outlined by our earlier research reports (Arisekar et al., 2022, ternal standard to check the analyte loss during the digestion of the
2023; Ulaganathan et al., 2022). A homogenized fish sample sample and check the accuracy of the instrument. The recovery per
(250 ± 5 mg) was weighed in a digestion vessel and predigested using centage of the internal standard was found to be 87.5–101.3 %, which
ultra-purified HNO3 (2.5 ml) for 90 min. Next, 7.5 ml Milli-Q water was was within the acceptable range of 80–120 %. Also, LOD and LOQ values
added to bring the total volume to 10 ml, and the sample was of Se and Hg in the current study were 0.13 and 0.11 µg/kg and 0.27 and
microwave-digested at 160 ◦ C for 20 min using a CEM microwave 0.16 µg/kg, respectively. Also, the coefficient of variance (CV%) of the
digestor (CEM Corporation Pvt. Ltd., USA). After digestion, the sample studied TEs (Se and Hg) were 3.4 and 4.1 %. The digestion efficiency,
was transferred to a new centrifuge tube, diluted with Milli-Q water up method suitability, and instrument accuracy were verified with analysis
to 50 ml, and stored at 4 ◦ C for 24 h or until analysis. Reagent and of European reference material (ERM BB 422) obtained from Merck Life
sample blank, as well as the certified reference material, were prepared Science Pvt. Ltd. RC% of the examined TE, Hg ranged from
and digested following the same procedure. The determination of the 104.8 ± 4.82 %, whereas Se was not present in the ERM. However, the
Table 1
Common and scientific name, length (cm), weight (g), family, habitat, feeding behavior (FB), and trophic level (TL) of analyzed fish.
Common Name Scientific Name Length Weight Family Habitat FB TL Major food
Indian anchovy Stolephorus indicus 11.7 ± 0.6 16.4 ± 3.94 Engraulidae Pelagic Herbivore 3.6 Zooplankton and phytoplankton
Indian oil sardine Sardinella longiceps 15.7 ± 1.2 28.4 ± 6.85 Dorosomatidae Pelagic Carnivore 3.59 Phytoplankton (especially diatoms) and
small crustaceans
Pinkhandle Sphyraena jello 30.2 ± 4.5 311 ± 15.7 Sphyraenidae Pelagic Carnivore 4.5 Fish and squid
barracuda
Ribbonfish Trichiurus lepturus 41.3 ± 3.7 224 ± 17.8 Trichiuridae Benthic Carnivore 4.4 Euphausiids, small pelagic planktonic
crustaceans and small fishes
Seerfish Scomberomorus 44.8 ± 7.4 1769 ± 24.7 Scombridae Pelagic Carnivore 4.5 Small fishes like anchovies, clupeids,
commersoni carangids
Little Tuna Ethynnus affinis 33.9 ± 4.1 647 ± 67.8 Scombridae Pelagic Carnivore 4.5 Fishes, crustaceans and squid
Emperor bream Lethrinus lentjan 19.8 ± 2.9 221 ± 23.8 Lethrinidae Benthic Carnivore 3.9 Crustaceans and mollusks
Rabbitfish Siganus javus 20.7 ± 2.7 158 ± 12.8 Siganidae Benthic Herbivore 2.4 Feeds on algae attached to the substrate
and on floating
Areolate grouper Epinephelus areolatus 31.7 ± 6.4 351 ± 20.2 Epinephelidae Benthic Carnivore 3.7 Fish and benthic invertebrates (prawns
and crabs)
Spottail needlefish Strongylura 28.3 ± 6.1 73.2 ± 9.8 Belonidae Pelagic Carnivorous 4.2 Small fishes, especially clupeoids
strongylura
Indian mackerel Rastrelliger kanagurta 20.7 ± 3.4 130 ± 10.6 Scombridae Pelagic Herbivore 3.2 Feed on phytoplankton (diatoms) and
zooplankton
Japanese threadfin Nemipterus japonicus 23.6 ± 4.3 176 ± 19.7 Nemipteridae Demersal Carnivore 4.1 Mainly on small fishes, crustaceans,
bream mollusks
Parrot fish Scarus ghobban 24.8 ± 2.6 190.4 ± 21.3 Scaridae Benthic Herbivore 2.0 Feed by scraping algae from rocks and
corals
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U. Arisekar et al. Food Research International 180 (2024) 114086
instrument accuracy was checked by analyzing other TE RC% values 2.4. Human health risk assessment (HHRA)
such as Cd (106.5 ± 6.7 %), As (89.6 ± 4.5 %), Cu (88.5 ± 2.7 %), Zn
(99.2 ± 3.5 %), and Fe (107.8 ± 8.1 %), which were found to be within TEs in seafood pose a severe threat to human and environmental
the acceptable range of 80–120 %, with a standard deviation of < 20 %. health around the world because these toxic substances can enter the
This proved the suitability of this method for the analysis of TE in fish body through seafood. HHRA is a common method for estimating the
and fishery products. potential harm associated with consuming food containing pollutants
(Kortei et al., 2020; Li et al., 2020). In this study, children (C) under the
2.3. Se and Hg risk–benefit assessment age of 7–10 years, women of childbearing/breastfeeding age (PW,
>18–30 years), and adults (A, >21 years) were studied to determine the
Kaneko and Ralston (2007) introduced the Se health benefit index (i. health hazards and benefits associated with Hg and Se intake through
e., Se-HBV), which measures the beneficial effects on health and the fish consumption, as these groups are considered at higher risk (EFSA,
negative risks to health (Leite et al., 2023). At first, it was believed that 2012, 2015). In this study, EFSA reference values were adopted for Hg
the dimension of the Se-HBV was proportionate to the anticipated and Se in fish and the following equations were used to determine the
benefits or harms of consuming fish/fish products containing different estimated intake (EI) of Hg and Se/meal, the target hazard quotient
concentrations of Se and Hg (Ralston, 2008). According to Ralston et al. (THQ), and hazard index (HI), referencing the guidelines provided by
(2016), the Se HBV index understates the minor nutritional benefits of the US Environmental Protection Agency (USEPA, 1991, 2011, 2012).
consuming excess Se. Recent studies have shown that the revised index
C × MS (or) intake rate
(HBVSe) more accurately represents the effective net content of Se in PWI (mg/meal) =
BW
commonly consumed foods (Ralston et al., 2016). As it is based on a
hypothesized biochemical process of Hg poisoning, the HBVSe serves as C × EF × MS × ED 3
an objective indicator for distinguishing between the impact of Hg ex THQ = × 10−
RfD × AT × BW
posures and dietary Se intakes.
Molar ratios of Se/Hg and Hg/Se were determined for all fish. The ∑
n
Se/Hg or Hg/Se molar ratio was determined by first dividing the Se Hazard index (HI) = THQHg + THQSe
concentration (mg/kg, wet weight) by the molar mass of 78.96 g/mol
i=1
and the Hg concentration by 200.59 g/mol, respectively. where C is the concentration of Se and Hg (mg/kg), and MS is meal
size (65 g for C and 130 g for PW, and 227 g for A) (USEPA, 1989, 2000).
mmol Se/kg BW is the average body weight (31.8 kg for C, 73 kg for PW, and 80 kg
Se/Hg molar ratio =
mmol Hg/kg for A) obtained from the Exposure Dose Guidance for Body Weight
provided by the Agency for Toxic Substances and Disease Registry
mmol Hg/kg
Hg/Se molar ratio = (ATSDR, 2023) and Exposure Factors Handbook by USEPA (2011). The
mmol Se/kg
HHRA was calculated under the assumption, as recommended by USEPA
(2000), that the ingested dose and absorbed doses are equal. The esti
Se Hg Se (or) Hg concentration in fish (mg/kg)
mmol or = mation of dietary exposure was based on the content of Hg and Se in raw
kg kg Molecular weight of Se (or) Hg
food, considering that all the Hg in marine fish is in the form of MeHg
The Se-HBV was evaluated according to Ralston (2008), and upda (EFSA, 2012, 2014). If the THQ is greater than the recommended
ted/revised HBVse was calculated based on Ralston et al. (2016) reference dosage (THQ/HI > 1), it indicates the potential occurrence of
recommendation. The Se and Hg values were expressed in mmol/kg for cumulative effects.
both equations, and their result was expressed accordingly. The Se/Hg The maximum safe consumption (CRlim ) limit indicates a safe intake
molar ratio has been a topic of study during the last decades using the Se- of fish per day, which considers the possible toxicity of each substance/
HBV (Ralston et al., 2019). Recently, Mirlean et al. (2019), Azad et al. element. The elements Se and Hg have their known RfD and their CRlim
(2019), and Grgec et al. (2020) studied the Se/Hg and Hg/Se ratios and was determined by applying the formula following USEPA (2000, 2011)
their associated health benefit value using the updated health risk index guidelines.
(HBVSe). Hence, considering the importance of the current equation and
RfD × BW
previous estimation methods, the health benefit index was calculated CRlim (kg/day) =
C
using both equations.
( ) ( ) The monthly fish meal consumption limit can be more easily defined
Se − HBV = (Se) ×
Se
molar ratio − (Hg) ×
Hg
molar ratio as the number of fish meals per month. The size of the meal is one factor
Hg Se in establishing the maximum daily intake. The average meal size was
( ) considered to be 8, 4.5, and 2.3 oz (0.227, 0.130, and 0.065 kg) for
Se − Hg
HBV Se = × (Se + Hg) adults, pregnant women, and children, respectively (USEPA, 2000).
Se
CRlim × T
The Se and Hg values applied in this calculation are expressed in CRmm (meals/month) =
MS
mmol/kg for both equations.
The absolute molar concentration of Se in the meal is determined by CRlim is the fish consumption limit, RfD is the reference dose of Se or
including Se in the fractional part, and the result also indicates the Hg (mg/kg), BW is the body weight (kg, children/pregnant women/
relative quantity of Se available in the meal. adult), C is the concentration of Se or Hg in fish (mg/kg), T is the number
of days per month (30.44 d/month), and MS is the average meal size (in
Relative Seavailablity =
Se − Hg kg).
Se
The free Se level in fish was calculated using a simple method by 2.5. Selenium risk– Benefit assessment
subtracting mmol Hg/kg from mmol Se/kg in food, as prescribed by
Ralston et al. (2019). The advantages of Se and possible hazards brought on by its related
TEs in seafood were assessed using ratios of actual intake (AIs) to rec
ommended daily intakes (RDIs) and upper limits (ULs) across various
age categories (Melgar et al., 2019). It is suggested that Se consumption
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U. Arisekar et al. Food Research International 180 (2024) 114086
satisfies the body’s physiological requirements when AI/RDI is more et al., 2023). Principal component analysis and dendrogram analysis
than 100 %. An AI indicates Se consumption below the recommended were also performed using Origin (Pro) (Feng et al., 2020; Pragnya et al.,
daily amount/RDI ratio of less than 100 %. Overconsumption of Se is 2021).
indicated by AI/UL ratio more than 100 %. Intakes of Se are deemed
within the safe range if the percentage difference between the AI and UL 3. Results and discussions
is less than 100.
3.1. Selenium concentration in marine fish
2.6. Fish consumption chart derivation following USEPA guidelines
The levels of selenium in marine fish varied between 0.203 and
The US Food and Drug Administration (USFDA) categorized each fish 0.470 mg/kg, with the lowest and highest concentrations found in
type by determining the maximum average Hg content that could be S. javus and S. longiceps, respectively (Table 2). The Se content of marine
consumed once, twice, and three times weekly without exceeding the Hg fish was found to be in the following order: S. longiceps > S. jello > E.
intake limit for an average body weight of children, pregnant women, affinis > S. commersoni > T. lepturus > R. kanagurta > N. japonicus > S.
and adults (USFDA, 2022). The present study compared the RfD value strongylura > S. indicus > E. areolatus > L. lentjan > S. ghobban > S. javus.
established by the US Environment Protection Agency (USEPA) to the Akin to the current study, Cabanero et al. (2005), Olmedo et al. (2013),
anticipated exposure from consuming various fish species to arrive at the and Lazarini et al. (2019) observed higher Se content in sardines,
maximum allowable intake level. The CRlim of fish associated with RfD S. longiceps (0.43 mg/kg), and S. pilchardus (0.37 and 0.45 mg/kg)
was calculated, aiming to help consumers cut down on Hg exposure collected from Spain, the Mediterranean Coast, and Brazil, respectively.
while still allowing them to obtain health advantages of consuming fish. Additionally, Mirlean et al. (2019) observed that horse mackerel
The limit of fish consumption of each fish was calculated using the (T. trachurus, 0.4 mg/kg), sardine (S. pilchardus, 0.4 mg/kg), and an
following equations: chovy (E. encrasicolus, 0.3 mg/kg) had the highest concentrations of Se,
which was consistent with the current findings. This investigation
RfDHg × BW
SV = revealed that the Indian oil sardine had a greater concentration of Se
CR (0.4 mg/kg) compared to the Indian mackerel (0.29 mg/kg). In a similar
(
28.3g
) vein, the Se concentration of S. longicpes obtained from the Portuguese
CR (g/week) = Serving size × Ounce per serving coast was found to be greater (0.5 mg/kg) than Mackerel (R. kanagurta,
oz
0.3 mg/kg), which aligns with the results presented in Table 2. The Box
× Serving per week
and Whisker plot showed that Se was almost symmetrically distributed
where SV is the threshold value for inclusion in a screening strategy in S. indicus (0.3 upper and 0.29 at lower quartile), T. lepturus (0.3 at
and CR denotes the weekly consumption rate. The USFDA recommends upper and 0.2 at lower quartile), R. kanagurta (0.35 upper and 0.32 at
2, 3, and 4 oz of fish and shellfish without sauce for children, pregnant lower quartile), and S. ghobban (0.4 upper and 0.39 at lower quartile).
women, and adults, respectively. The FDA/EPA technical advisory note Conversely, other fishes such as S. longiceps, S. jello, E. affinis, L. lentjan,
on fish consumption states that fish with a maximum average Hg level of E. areolatus, and S. strongylura showed positive skewness, showing the
0.15 mg/kg when eating three servings per week falls into the “Best majority of the distribution occurred below the median value of Se at
Choice Fish” category, allowing for 2–3 servings/week. Fish with Hg each species. In contrast, S. commerson, S. javus, and N. japonicus showed
concentration in the range of 0.15 to 0.24 are considered to be “Good negative skewness, with the majority of the distribution occurring above
choices,” permitting 1–2 serving/week. The consumption of three the median value of Se (Fig. 1).
servings per week is not advised for these fish. If the SV value of Hg in a In relation to habitat, it was noted that the concentration of selenium
certain fish is more than 0.46 mg/kg, it is classified as a “Choice to was higher in pelagic fish, ranging from 0.278 to 0.470 mg/kg, with the
Avoid” species (USFDA, 2022). lowest and highest values recorded for S. indicus and S. longiceps,
respectively. On the other hand, benthic fish exhibited a Se concentra
2.7. Statistical analysis tion ranging from 0.203 to 0.294 mg/kg, with the minimum and
maximum values observed in S. javus and T. lepturus, respectively. The
The raw Se and Hg data were analyzed using Microsoft Excel, and the demersal fish (N. japonicus) had a moderate concentration of Se at
findings are shown as a mean ± SD (Table 2). Box and Whisker and 0.282 mg/kg. Se levels in fish were observed in the following sequence:
Person correlation analyses were performed using Origin (Pro) software pelagic > demersal > benthic. The Pearson correlation coefficient in
(v 2022; OriginLab Corporation, Northampton, MA) to examine the dicates a positive correlation between habitat and Se concentration
prevalence of Se and Hg in marine fish and the association between Se (p = 0.671). According to recent studies (Kehrig et al., 2013; Seixas
and Hg content in fish and their size (Kalisinska et al., 2017; Parker et al., 2014), Se and Hg concentrations are higher in pelagic fish than in
Table 2
Se and Hg concentration in marine fish and their molar ratio calculation and Se:Hg health benefit/risk estimation (Se-HBV and HBVse).
Fish Se (mg/kg) Hg (mg/kg) MRLHg Se μmol/kg Hg μmol/kg Ratio Hg/Se Ratio Se/Hg Se-HBV HBVse Free Se R-Se
S. indicus 0.278 0.048 0.5 3.52 0.24 0.07 14.6 51.28 3.50 3.28 0.93
S. longiceps 0.470 0.031 0.5 5.95 0.16 0.03 38.0 226.1 5.95 5.80 0.97
S. jello 0.365 0.056 0.5 4.63 0.28 0.06 16.7 77.35 4.61 4.35 0.94
T. lepturus 0.294 0.043 0.5 3.72 0.21 0.06 17.6 65.36 3.71 3.51 0.94
S. commersoni 0.319 0.028 0.5 4.05 0.14 0.03 29.4 119.0 4.04 3.91 0.97
E. affinis 0.348 0.106 1.0 4.41 0.53 0.12 8.31 36.58 4.35 3.88 0.88
L. lentjan 0.242 0.063 1.0 3.07 0.32 0.10 9.70 29.74 3.04 2.75 0.90
S. javus 0.203 0.097 0.5 2.57 0.48 0.19 5.31 13.55 2.48 2.09 0.81
E. areolatus 0.258 0.048 0.5 3.26 0.24 0.07 13.7 44.60 3.25 3.02 0.93
S. strongylura 0.280 0.042 0.5 3.55 0.21 0.06 16.8 59.61 3.54 3.34 0.94
R. kanagurta 0.290 0.037 0.5 3.68 0.19 0.05 19.7 72.37 3.67 3.49 0.95
N. japonicus 0.282 0.039 0.5 3.58 0.20 0.05 18.2 65.11 3.57 3.38 0.95
S. ghobban 0.204 0.026 0.5 2.58 0.13 0.05 20.0 51.66 2.57 2.45 0.95
R-Se – Relative selenium availability; MRLHg – Maximum residual limit of Hg (EC1881/2006 & FSSAI, 2011).
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Fig. 1. Box and Whisker plot showing the distribution of Se and Hg in fish.
demersal fish and benthic fish, which provides evidence for this argu lower trophic levels < 3.0. S. javus and S. ghobban had lower Se con
ment. In connection with eating behavior based on TL, Se concentration centrations in comparison to other fish species, potentially attributable
in fish was shown to be high in higher trophic levels species such as to their lower TL (<3.0). A positive association (51 %) between TL and
carnivores and predators while low in herbivores, notably in those with Se concentration in fish was confirmed by Pearson correlation analysis.
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U. Arisekar et al. Food Research International 180 (2024) 114086
Similarly, Mason et al. (2000), Kalisinska et al. (2017), and Parker et al. minimum and maximum. Outliers are displayed as tiny squares and are
(2023) investigated the correlation between TEs (including Se and Hg in set out above or below the box at a distance greater than 1.5 times the
fish) and reported that there was a positive relationship between TE interquartile range. Extreme outliers are positioned more than 3 stan
concentration and feeding behavior and TL. A previous study found that dard deviations outside the box. Box and whisker plots revealed statis
highly carnivores (TL > 3.0) and predators (TL > 4.0) can accumulate tical evidence that Se and Hg were not distributed uniformly among fish
more trace elements through biomagnification than herbivores, primary species (Fig. 1). The Pearson correlation analysis showed a positive
carnivores, and omnivores, which may be the possible explanation for connection (p < 0.05) between the Hg levels in pelagic and benthic fish.
higher Se concentration in fish with TL > 3.0 than fish with TL value 3.0. In agreement with these findings, Cammilleri et al. (2019) and Hilgen
The current study observed a favorable link between the concentration dag et al. (2022) observed that the average concentration of Hg in
of Se in fish and both their length and weight. Concurrently, Yi and pelagic fish was greater than that in demersal and benthic fish.
Zhang (2012), Jiang et al. (2016), and Luczynska et al. (2018) investi Conversely, Storelli et al. (1998), Storelli (2008), and Bonsignore et al.
gated the relationship between TE concentration in fish and size and (2013) identified higher concentrations of TEs in benthic fish compared
discovered a positive correlation between TE concentration and fish to pelagic and demersal fish. A few researchers have found that demersal
size, which contrasts with the findings from studies by Farkas et al. fish had greater TE concentrations than benthic or pelagic fish (Ahmad
(2000), Obaidat et al. (2015), Sallam et al. (2019), and Javanshir Khoei et al., 2015; Di Lena et al., 2017; Grgec et al., 2020). The variations in
(2023). Therefore, due to inconsistencies found in past studies, it is research outcomes regarding the TE concentration in pelagic and
recommended that a more comprehensive investigation be conducted to benthic fish can be attributed to factors such as TL, foraging behavior,
validate the factual connection between size and TE content. and method, the degree of contamination of the region, anthropogenic
activities in the area, fishing activity, and the propensity of Hg bio
3.2. Mercury concentration in marine fish magnification in the food web (Grgec et al., 2020). This study revealed a
negative relationship between the concentration of Hg and the size of
Hg level in the muscle tissue of marine fish collected within the fish (length and weight) (Fig. 2).
designated study region exhibited significant variation, ranging from In addition, a weak positive connection was noticed between the TL
0.024 to 0.106 mg/kg (Table 2). The minimum and maximum concen and Hg content in fish. These findings align with previous research
trations were observed in S. ghobban and E. affinis. It was seen that about conducted by Yi and Zhang (2012), Obaidat et al. (2015), and Luczynska
69.2 % examined samples exhibited a Hg concentration below 0.05 mg/ et al. (2018), who examined the concentration of TEs in fish from
kg. Furthermore, 23.1 % of the fish sample under investigation showed various locations including China, Poland, and the Indian Ocean. These
Hg levels varying from 0.05 to 0.1 mg/kg. Conversely, E. affinis studies also reported a negative correlation between TEs and fish size
exhibited Hg concentrations beyond 0.1 mg/kg. In contrast, Mirlean (length and weight), as well as TLs. Nevertheless, several researchers
et al. (2019) observed that 60 % of the sample had Hg concentrations have documented a positive association between the concentration of
over 0.1 mg/kg, a value that was three times greater than that reported TEs in fish and their size and TL (Seixas et al., 2014; Kalisisnska et al.,
in the present study. Additionally, they found that 25 % of the fish 2017). In addition, Javanshir Khoei (2023) found a negative relation
collected from the Brazilian coast had Hg levels below 0.05 mg/kg, ship between habitat and TE levels but a positive correlation between TE
which aligns with the findings of the present investigation. Contrary to concentration and fish size, as well as metabolic rate. Therefore, in light
the Brazilian coast, the samples obtained from the southeastern coast of of the discrepancies observed between the research findings presented in
India exhibited lower concentrations of Hg, suggesting a lesser degree of this study and previous studies, it is recommended that future in
TE pollution. This finding implies a higher level of safety associated with vestigations focus on conducting comprehensive studies to elucidate the
seafood products obtained from this particular region. Interestingly, the mechanisms underlying accumulation kinetics. This will contribute to a
Hg concentration in S. jello, E. affinis, and E. areolatus was 0.3, 0.1, and deeper understanding of the potential for accumulation, as well as the
0.2 folds lower whereas S. gibbose, L. lentjan, and S. strongylura had factors that influence bioaccumulation, particularly in relation to
slightly higher concentrations compared to a previous study conducted habitat, TL, and fish size. A few authors suggested that actual Hg
at the Tuticorin coast (Shalini et al. 2021a). Similar to this, Hg con contamination in the area and the amount of anthropogenic load in the
centrations were found to be 5- and 4.5-fold higher than those obtained
in the current study in grouper (Epinephelus sp.) and L. lentjan collected
from the Tuticorin coast of Tamil Nadu. Hg concentrations in marine
fishes were significantly lower than the maximum residual limit (MRL)
of 0.5 mg/kg for most fish and 1.0 mg/kg for predatory fish (tuna,
swordfish, mullet, and some reef fishes) set by the European Commission
(EC/1881/2006) (EC, 2006, 2022) and the Food Safety Standard Au
thority of India (FSSAI, 2011). It is not surprising that tuna exhibited
higher Hg levels (0.106 mg/kg) because of its TL (feeding behavior). In a
similar vein, Grgec et al. (2020) showed elevated Hg concentrations in
tuna among the 12 studied marine fish obtained from the Eastern
Adriatic Sea. In accordance with the habitat, pelagic fish showed the
higher level of Hg with a mean value of 0.05 mg/kg, followed by benthic
fish with a value of 0.036 mg/kg, and demersal fish with a value of
0.03 mg/kg.
Box and Whisker plot revealed that the distribution of Hg concen
tration in E. affinis and S. longiceps was roughly symmetrical, whereas it
was positively skewed in S. indiicus, S. jello, L. lentjan, S. javus,
R. kanagurta, and S. ghobban, and negatively skewed in T. lepturus,
S. commerson, E. areolatus, and S. strongylura. The rectangular portion of
the plot encompasses the middle half of each sample and travels from
the lower to the upper quartile. The center lines inside each box indicate
the sample median locations. With the exception of any outside or high Fig. 2. Pearson correlation analysis of Se and Hg in fish and their length,
outliers, the whiskers in each sample extend from the box to the weight and trophic level.
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U. Arisekar et al. Food Research International 180 (2024) 114086
Fig. 3. Correlation of Se and Hg molar ratios and their length and weight and health benefit indices.
area may have an impact on fish Hg content instead of their larger size whereas the Hg concentration in fishes exhibited a higher degree of
and higher TL fish collected from un/less polluted region, which may be variation (4.1-fold). Similar patterns of fluctuations between Se and Hg
the cause of the discrepancy in previous studies (Burger and Gochfeld, concentrations in fish have been observed in other places (Karimi et al.,
2012; Yi and Zhang, 2012). 2013; Azad et al., 2019).
Furthermore, Grieb et al. (1990) emphasized that the significance of A dendrogram was constructed to depict the similarity of Se and Hg
harmful TE concentration in aquatic species depends on the phys concentrations among the fish samples. It was noted that the samples
icochemical characteristics of the water and its environment (pH, acid- formed three distinct clusters. The majority of the fish species were
neutralizing activity, bloom level, total phosphorous, nitrogen, organic classified within cluster 1, exhibiting a similarity of over 95 % (Fig. 5).
load, sulfate, conductivity, dissolved organic solids). Meanwhile, Wang However, S. stongylura and S. jello formed a secondary cluster along with
and Rainbow (2008) pointed out the difficult nature of explaining the a primary cluster with a similarity of > 85 %. A third cluster was
evolutionary basis for the bioaccumulation of TEs in aquatic organisms. observed between the second cluster and S. commerson, displaying a
Both physiological/biochemical process and metal geochemistry are similarity of less than 20 %, suggesting that the concentration of Se and
responsible for differences in the TE concentration observed in different Hg significantly differed from that of other fish species, while the levels
aquatic species as well as freshwater and marine species. Further, dif in the remaining fish species were relatively similar (Fig. 5 and Table 6).
ferences in the accumulation and elimination patterns of metals are also The variation in fish TE concentrations in TLs and living habitats
influenced by contrasting behaviors of different species. However, (pelagic, benthopelagic, and demersal) was examined using principal
Mackay et al., (2016, 2018) affirm that bioaccumulation of fish depends components analysis (PCA). Fig. 4 shows that the first two axes of the
on temperature (on the species present), nature of food, and feeding PCA accounted for 63.77 % of the variance in TE concentrations across
behavior. The authors noted that bioaccumulation of TEs is majorly the fish samples (Table 6). The scree plot demonstrated that the eigen
influenced by contaminants come from the diet of fish, spatial variation, value starts from the straight line up to PC2, and the eigenvalue grater 1
chemical fate process, stratification, biotransformation rate, and sedi was taken for PCA analysis. PC1 explained 41.42 % variation, with a
ment water fugacity ratios. Hence, interpretation of these observation moderate loading of Se and strong loadings of L, W, and TL, whereas PC2
requires a detailed understanding of the ecosystem/sampling point, explained 22.34 % with a strong loading of Se and Hg, a moderate
biokinetic models, local hydrodynamic and the species in that loading of TL, and a negative loading of L and W. The PCA plot revealed
ecosystem, geochemistry of metal, and predatory–pray interaction. that the loading of pelagic and benthic fish species was comparable;
Therefore, an attempt was made based on the previous findings dis however, the loading of demersal fish differed significantly. The loading
cussed earlier and it was hypothesized that the concentration of TEs in plot revealed that demersal fish were loading over pelagic and benthic
aquatic organisms is mostly influenced by their physicochemical fea fish, owing to the larger variation in the data set. Demersal fish showed
tures, nature of food/feeding habit and their contamination level, dif greater variance and were located at the upper and lower sides of PC2
ference in accumulation pattern of fish species, and the extent of whereas pelagic and benthic fish were located in the middle of PC1 and
anthropogenic activities rather than the length and weight of the fish PC2, indicating a distinct gradient along PC1 in Se and Hg concentra
(Wang and Rainbow, 2008; Mackay et al., 2018). In the current inves tions among different habitat preferences. However, high loads of Se and
tigation, it was revealed that the variation in selenium (Se) levels among Hg were found on the positive axis of PC1 in pelagic fish, but PC1 and
the analyzed fish was comparatively lower (twofold) when compared to PC2 were negatively loaded in benthic fish. These findings suggested a
that in Hg concentrations. Specifically, the difference between the high degree of species variety in connection to the various region
maximum and minimum Se concentrations in marine fish was less, sources for these TEs. Similar to the current findings, Feng et al. (2020)
8
Table 3
U. Arisekar et al.
Health risk assessment (target hazard quotient, hazard index, and consumption limit of fish and meals) of trace metals in marine fish.
Risk factor THQse THQHg HIse+Hg CRlim - Se CRlim - Hg CRmm - Se CRmm - Hg
Fish C PW A C PW A C PW A C PW A C PW A C W A C W A
S. indicus 0.11 0.10 0.16 0.49 0.43 0.52 0.61 0.53 0.67 0.58 1.31 1.44 0.07 0.15 0.17 270 308 193 31.0 35.3 22.2
S. longiceps 0.19 0.17 0.27 0.32 0.28 0.34 0.51 0.45 0.60 0.34 0.78 0.85 0.10 0.23 0.25 159 182 114 47.6 54.3 34.1
S. jello 0.15 0.13 0.21 0.57 0.50 0.59 0.71 0.62 0.80 0.44 1.00 1.09 0.06 0.13 0.14 205 234 147 27.0 30.8 19.3
T. lepturus 0.12 0.10 0.17 0.43 0.38 0.45 0.55 0.48 0.62 0.54 1.24 1.36 0.08 0.17 0.19 255 291 182 35.2 40.2 25.2
S. commersoni 0.13 0.11 0.18 0.28 0.25 0.29 0.41 0.36 0.48 0.50 1.14 1.25 0.12 0.26 0.29 235 268 168 54.3 62.0 38.9
E. affinis 0.14 0.12 0.20 1.08 0.95 1.13 1.23 1.07 1.33 0.46 1.05 1.15 0.03 0.07 0.08 215 245 154 14.1 16.1 10.1
L. lentjan 0.10 0.09 0.14 0.65 0.57 0.68 0.74 0.65 0.81 0.66 1.51 1.65 0.05 0.12 0.13 309 353 221 23.6 27.0 16.9
S. javus 0.08 0.07 0.12 0.99 0.87 1.03 1.07 0.94 1.15 0.79 1.80 1.97 0.03 0.08 0.08 369 421 264 15.4 17.6 11.0
E. areolatus 0.10 0.09 0.15 0.49 0.43 0.51 0.59 0.52 0.66 0.62 1.42 1.55 0.07 0.15 0.17 291 332 208 31.3 35.7 22.4
S. strongylura 0.11 0.10 0.16 0.43 0.38 0.45 0.55 0.48 0.61 0.57 1.30 1.43 0.08 0.17 0.19 267 305 191 35.3 40.3 25.3
R. kanagurta 0.12 0.10 0.16 0.38 0.33 0.40 0.50 0.44 0.56 0.55 1.26 1.38 0.09 0.19 0.21 258 294 185 40.0 45.6 28.6
N. japonicus 0.11 0.10 0.16 0.40 0.35 0.42 0.52 0.45 0.58 0.57 1.29 1.42 0.08 0.19 0.20 265 303 190 38.0 43.4 27.2
S. ghobban 0.08 0.07 0.12 0.26 0.23 0.28 0.35 0.30 0.39 0.78 1.79 1.96 0.12 0.28 0.31 368 419 263 57.9 66.1 41.5
THQ- Target hazard quotient; HI – Hazard index; CRlim - Maximum allowable fish consumption rate (kg/d); CRmm - Fish meal consumption limit (meals/month); C-.
Children; PW- Pregnant women; A- Adult.
9
Brazil.
with habitat and trophic level.
the Hg/Se molar ratio in marine fish ranged from 0.03 to 0.19, with
habitat, pelagic fish had the greatest Se/Hg molar ratios (8.3–38), fol
a Se/Hg ratio greater than 1 and that pelagic fish had a higher Se/Hg
variation in the fish species was largely influenced by pollution, with
and feeding behavior. In addition, Cabrini et al. (2018) reported that TE
ratio (9–66) than benthic (3–8) and demersal fish (1.4–2.5). In addition,
current study, Grgec et al. (2020) observed that all the analyzed fish had
The molar ratio of Se/Hg and Hg/Se exhibited considerable variation
relative Se in fish and the molar concentrations of Se, which ranged from
63 to 55 % and 47 to 63 %, respectively. The current study found that all
analyzed fish had Se-HBV and HBVse values > 1, demonstrating that the
consumption of seafood may have a beneficial impact on levels of Se and
a potential protective effect against Hg poisoning. There was a corre
lation between the length and weight and the concentrations of free and
relative Se in the fish. Similar studies were carried out by Mirlean et al.
(2019) and Kehrig et al. (2013) on the health benefits of Se in com
mercial fish species caught off the coast of the Atlantic Ocean and in Kio-
de-Janeiro (Brazil). According to reports, mean Se-HBV and HBVse
values over 1 indicate a positive effect of Se and a neutralizing effect on
Hg. These findings point to a strong potential for protection against Hg
hazards from seafood consumption. The consideration of fish with a
large Se-HBV value should be addressed cautiously due to the poten
tially harmful effects associated with high Se concentration. In this
study, researchers utilized the recently created HBVse index by Ralston
et al. (2016) to evaluate seafood safety in the subtropical region of the
SECI. This marks the first instance of using this index in such an
assessment. The fish that were examined did not exhibit a negative
HBVse value (as shown in Table 2), indicating that the ingestion of these
fish may counteract the potential risks linked with exposure to Hg. Thus,
all three indicators support the health advantages and safety of fish
Fig. 5. Dendrogram showing the similarity of Se and Hg concentration in fish. consumption. Supporting this statement, Parizek and Ostadalova (1967)
reported that Se may be able to protect against Hg poisoning, and fur
respectively. The lowest and highest Hg/Se ratios were inversely ther research has supported this claim (Ralston, 2008; Ralston et al.,
correlated with Se content and potentially linked to Hg concentration in 2008). Instead of focusing solely on the concentration of Hg, several
fish (p < 0.05). According to previous studies, Se/Hg ratios > 1 and Hg/ researchers have turned to using the Se health benefit index as a
Se 1 indicate a health benefit of Se and a protective effect of Se on Hg straightforward indicator of both hazards and benefits (Looi et al., 2016;
toxicity, whereas Se/Hg ratios 1 and Hg/Se > 1 indicate a higher Hg Mirlean et al., 2019). This research, which focuses on marine fish safety
toxicity compared to a health benefit and a protective effect of Se on Hg and health benefits, does not cover all possible health risks and solely
toxicity associated with seafood consumption. addresses other safety and quality parameters. Organic compounds and
The current investigation confirmed that all fish collected in this other TEs in marine fish should be studied in the future.
region were safe for consumption and had increased health benefit po The HBVse values of all the analyzed fish species ranged from 2.48 to
tential due to the Se/Hg ratios being > 1 and the Hg/Se ratios being 5.95, which is substantially higher than 1. It has been hypothesized that
much below 1. In agreement with the present study, Mirlean et al. this finding will provide some measure of protection against Hg
(2019), Melgar et al. (2019), and Grgec et al. (2020) reported higher Se/ poisoning (Ralston et al., 2016). Fish species off the coast of southeast
Hg molar ratios (>1) and lower Hg/Se molar ratios (<1) in marine fish India were analyzed for their toxicological and nutritional effects on
collected from Brazilian Atlantic Coast, Lugo city (Spain) and Adriatic children, women, and adults. Table 4 shows the results of a benefit–risk
Sea. The authors concluded that marine fish consumption provides a analysis, revealing that the Se intakes of all age groups were within or
higher Se beneficial effect and protective effect against Hg toxicity, below the UL. The ratios of AI/RDI for children, pregnant women, and
attributed to the higher Se and lower Hg concentrations in fish. Fig. 3 adults varied between 107.1 and 248.1, 73.7 and 170.9, and 117.5 and
displays the results of a Pearson correlation study showing a modest 272.3, respectively. These findings suggest that the intake of Se
relationship between the Se/Hg ratio and the sizes of the fish. Likewise, adequately fulfills the physiological needs of individuals across all age
Hg/Se ratios exhibited a negative association with both the length and categories. However, the consumption of E. affinis (88.03 %), S. javus
weight of the samples. The molar concentration of Se exhibited a posi (93.6 %), L. lentjan (73.7), N. japonicus (74.1 %), and S. ghobban (92.9 %)
tive correlation of 66 % with Se/Hg molar ratios and a negative corre for pregnant women was somewhat lower than the RDI, indicating that
lation with Hg/Se ratios. Conversely, the molar concentration of Hg people should increase their Se intake to meet their dietary re
showed a negative association of − 75 % with Se/Hg ratio and a positive quirements. Therefore, the current study advises pregnant women to
correlation of 89 % with Hg/Se ratios. It was observed that the Se/Hg consume S. longiceps, S. indicus, S. jello, T. lepturus, S. commersoni,
molar ratios exhibited a slight decrease as the length and weight of the E. areolatus, S. stronggylura, and R. kanagurta to meet the daily recom
fish increased. This decrease could be attributed to the elevated con mended value of Se for the systematic physiological and biological
centration of Hg in the fish, which demonstrates the protective role of Se functions. The AI/UL ratio of 100 indicates that Se consumption is below
(Azad et al., 2019; Grgec et al., 2020). the safe level, whereas > 100 indicates that Se consumption may exceed
the upper limit and that such food should be restricted. In the current
3.4. Benefit–risk assessment and consumption advisories investigation, the AI/UL ratios for children, pregnant women, and adults
ranged from 45.3 to 104.9, 17.2 to 39.8, and 27.4 to 63.5, respectively,
Se-HBV and HBVse were calculated using the molar ratio of Se and demonstrating that Se consumption did not increase significantly above
Hg, and the results are shown in Table 2. The values of the Se-HBV and 100 %, and thus all of the analyzed fish were safe and recommended for
HBVse indexes varied from 13.5 to 226.1 and 2.48 to 5.95, respectively, consumption.
with the minimum and greatest values observed for S. javus and Fish consumption advisories have been developed using the
S. longiceps, which may be related to the higher Se concen screening value (SV) from consumption patterns of various fish species.
tration compared to Hg level. The results of the Pearson correlation A field study was undertaken to determine the estimated intake of
analysis showed that fish Hg levels and Se concentrations had a negative people living around the Tuticorin coast, and SVs for each fish were
connection (− 15 to − 52 %), whereas HBVse and Se-HBV exhibited a determined based on the intake level (ounce/week) (Table 5). The SVs
positive association (83–100 %) with fish Se concentrations. Similar to were calculated for children (32 kg), adults (80 kg), and pregnant
this, there was a strong correlation between the amounts of free and women (73 kg). According to the EPA/FDA fish consumption guidelines,
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Table 4
Health benefit assessment of selenium intake (mg/kg) using actual intake (AI), recommended daily intake (RDI) and upper limit (UL).
Intake Se AIC AIW AIA AIC: RDIC AIW: RDIW AIA: RDIA AIC: ULC AIW: ULW AIA: ULA
Fish 0.278 0.564 0.495 0.788 146.5 100.9 160.8 61.99 23.55 37.52
S. indicus 0.470 0.955 0.837 1.334 248.1 170.9 272.3 104.9 39.87 63.53
S. longiceps 0.365 0.742 0.651 1.037 192.8 132.8 211.6 81.56 30.98 49.37
S. jello 0.294 0.597 0.524 0.834 155.2 106.9 170.3 65.65 24.94 39.74
T. lepturus 0.319 0.649 0.569 0.906 168.5 116.1 185.0 71.31 27.09 43.17
S. commersoni 0.348 0.707 0.620 0.988 183.7 126.5 201.6 77.72 29.53 47.05
E. affinis 0.242 0.492 0.431 0.687 127.8 88.03 140.3 54.07 20.54 32.73
L. lentjan 0.203 0.412 0.361 0.576 107.1 73.75 117.5 45.30 17.21 27.42
S. javus 0.258 0.523 0.459 0.731 135.9 93.63 149.2 57.51 21.85 34.81
E. areolatus 0.280 0.570 0.500 0.796 148.0 101.9 162.4 62.61 23.79 37.90
S. strongylura 0.290 0.590 0.517 0.824 153.2 105.5 168.2 64.82 24.62 39.24
R. kanagurta 0.282 0.574 0.503 0.801 149.0 102.6 163.5 63.03 23.95 38.15
N. japonicus 0.204 0.414 0.363 0.578 107.5 74.08 118.0 45.50 17.28 27.54
S. ghobban 0.256 0.519 0.455 0.726 134.9 92.93 148.1 57.08 21.68 34.55
AI – Actual intake of Se (mg/week); C- Children; W- Pregnant Women; A- Adult; AI:RDI – Ratio of AI and RDI (0.055 mg/d for C & 0.07 mg/d for W and A, which was
converted to per week) obtained from EFSA (2017); AI: UL- Ratio of AI and UL (0.2 mg/d for C and 0.3 mg/d for W and A) obtained from EFSA (2006).
Table 5
Screening value of Hg (mg/kg) with the comparison of FDA/EPA fish consumption advisories.
Fish Hg Ounce Child Women Adult Category of fish FDA/EPA consumption advisories
SV of Hg detected below 0.15 mg is considered “Best Choice Fish.” In the complying with USEPA guidelines. The THQ value of Se for C, PW, and A
current study, the SVs of Hg for children from marine fish consumption through fish consumption ranged from 0.08 to 0.19, 0.07 to 0.17, and
ranged from 0.03 to 0.11 mg/kg, indicating that children can safely 0.12 to 0.27, respectively, whereas the THQ value of Hg (except
consume > 3 servings/week without adverse health effects and that 3 E. affinis) ranged from 0.26 to 0.99 for C, 0.23 to 0.95 for PW, and 0.28
servings/week of fish consumption is sufficient to meet the nutritional to 0.99 for A. Similarly, HI ranged from 0.35 to 0.74 for C, 0.30 to 65 for
needs of children for growth and metabolism. Similarly, the SV of Hg PW, and 0.39 to 0.81 for A. According to the USEPA standard criteria,
through fish consumption was found to be between 0.15 and 0.23 mg, the estimated THQ (E. affinis) and HI values were 1 (E. affinis and
indicating that the fish can be consumed in 2–3 servings per week S. javus), indicating that ingestion of the fish examined had no carci
without negative health effects and is considered a “Good Choice.” Still, nogenic health impacts. Similar to the current study, Kortei et L. (2020)
it is not recommended to consume more than 3 servings per week. In the in O. niloticus and C. anguillaries collected from Southern Ghana, Özden
current study, the SVs of Hg from S. indicus and S. longiceps consumption et al. (2020) in aqua-cultured bluefin tuna, and Ulusoy (2023) in tuna
for children, women, and adults ranged from 0.03 to 0.09, indicating species analyzed the TEs and found that the THQ/HI value of Hg
that these fish fall into the Best Choice category and > 3 servings/week was > 1, indicating possible noncancerous risk. Meanwhile, Sadeghi
can be consumed without health consequences while meeting nutri et al. (2020), Altınok-Yipel et al. (2022), and Arisekar et al., (2023,
tional requirements. The SVs of Hg for all other fish, suggesting con 2024) have demonstrated that intake of tuna and tuna products from
sumption of 1–2 servings/week (Table 5), varied from 0.06 to 0.28 mg, local markets in Oman, Istanbul, and the Tuticorin coast (India) does not
demonstrating that children and adults (including women) may pose carcinogenic risk because of THQ/HI < 1. The HRA investigation
consume 2–3 servings/week and 1–2 servings/week with health bene suggests that long-term ingestion of E. affinis and S. javus may pose
fits, falling within the Good Choice category (USFDA, 2022). The overall chronic toxicity to humans. However, the Se/Hg molar ratio, Se-HBV,
results show that fish collected from the GoM region had lower Hg and HBVse indicate that Se show a protective behavior of Hg toxicity
concentrations, which led to all fish being listed under the Best Choice to in fish. It was determined that the Hg concentrations in fish from this
Good Choice category according to EPA/EDA fish consumption advi region were found to be lower than the MRL specified by the EC (2006,
sories and found safe for consumption with achieving nutrient re 2022) and FSSAI (2011), making them safe for consumption. CRlim was
quirements. None of the fish exceeded the Choice to Avoid category, calculated using USEPA (2000) guidelines, and it was discovered that
which is the SV of Hg is 0.46 mg for a single serving/week. the Se fish consumption limit ranged from 0.34 to 0.79 kg/d for C, 0.78
to 1.80 kg/d for PW, and 0.85 to 1.97 kg/d for A, whereas the Hg
3.5. Health risk assessment (HHRA) consumption limit ranged from 0.03 to 0.12 kg/d for C, 0.07 to 0.28 kg/
d for PW, and 0.08 to 0.31 kg/d for A. This study found that adults can
The health risk of the fish-consuming population, which included take about 1–2 kg/d of fish without having any health consequences;
children (C), pregnant women (PW), and adults (A), was determined however, Hg has a lower consumption limit due to lower RfD and higher
using the THQ and HI for both Se and Hg concentration in fish, toxicology when compared to Se. The RfD for Se was 0.005 mg/kg/
11
U. Arisekar et al. Food Research International 180 (2024) 114086
d whereas that of Hg was 0.0001 mg/kg/d, which was 50 times lower disease), and Se helps treat or prevent this condition (Jia et al., 2023).
than the RfD for Se. Regarding the lower consumption rate of fish with Hg is one of the most easily absorbed TEs found in nature. It is one of the
respect to Hg concentration, the lower RfD and higher Hg toxicity were TEs that continues to accumulate up to 95–97 % of the Hg in fish muscle
significant factors that substantially influenced the consumption limit. tissue compared to other organs (EFSA, 2012, 2015). To protect humans
Recently, Li et al. (2020) conducted the HRA through TEs via fish con and animals from Hg toxicity, the USEPA and EC set a water/sed
sumption. The authors reported that the lower RfD value of TE was due iment quality standard for aquatic organisms and an MRL for edible fish
to its higher toxicity, which influenced the HRA estimation (reflected in tissue intended for human consumption.
higher THQ and HI), leading to restriction/reduction in the consumption Exposure to Hg in at-risk populations might be reduced if high
limit and pattern compared to other elements (Zheng et al., 2007). ambient concentrations of Se prevent bioaccumulation and bio
To accurately assess and characterize the potential hazards to human magnification of Hg in aquatic food webs. The spread of mercury is
health, it is necessary to know the maximum amount of fish/fish meal restricted to the following TL due to the mediation of Hg burdens
that can be consumed safely over a specific period without adverse ef in animals/humans (Gerson et al., 2020). Similar to the last case, the
fects, considering exposure evaluation. Table 3 illustrates the maximum majority of the data supporting this concept come from experiments
daily fish consumption limit (g/d) as well as the number of times per conducted on model mammalian species. Hg sequestration or redistri
month that a supper containing 0.227 kg of fish is acceptable for an bution in vivo in response to higher Se exposures lends credence to this
adult, 0.065 kg for children, and 0.135 kg for women of reproductive theory. Toxic levels of Hg in animals may be reduced by co-
age. The maximum recommended intake of fish meals for children, administering Se and Hg (Gerson et al., 2020; Zampetti and Brandt,
pregnant women, and adults for Se is greater than 100 meals per month, 2023), and the unique chemical properties of Se cause Hg to become
whereas that for Hg is greater than 30 meals per month for children, 16 insoluble. Se precipitates in the liver and kidney, which is crucial for the
meals per month for pregnant women, and 20 meals per month for elimination processes. These data show that Se in molar excess of > 1
adults. However, the consumption limit for E. affinis and S. javus was demethylates or renders Hg physiologically unavailable for in vivo
lower for both children (14 and 15 meals/month) and adults (10 and 11 methylation. Higher trophic species may bioaccumulate less Hg due to
meals/month). This study suggests restricting consumption of E. affinis Se-mediated demethylation, redistribution, and sequestration (Yin et al.,
and S. javus to between 10 and 14 and 11 and 15 means per month for 2020; Tan et al., 2022). Associative data suggest that Se mediates Hg in
adults and children, respectively, taking into account the toxicity of Hg. food webs at the ecological level. The control of Hg bioaccumulation and
However, the consumption limit for all other fish was determined to be retention by Se, and its implications for Hg trophic transmission in
greater than 16 meals per month, indicating that marine fish collected in aquatic food webs, is appears to be a complicated process in research
this region can be consumed safely by children, pregnant women, and involving aquatic animals and ecosystems (Kho et al., 2022). Minimizing
adults. Researchers investigated the human health consequences of microbial Hg methylation might be an efficient strategy for reducing Hg
ingesting TEs through fish and concluded that children and pregnant levels entering food webs because this process is responsible for Hg
women were more susceptible to TEs due to Hg toxicity (Welch et al., biomagnification in aquatic food webs (Yin et al., 2020). Inhibition of
2020; Jia et al., 2023). The guidelines aim to help people reduce their Hg methylation by SeIV has been supported by mechanistic evidence in
exposure to Hg while still receiving the health benefits associated with many investigations. Photochemical demethylation of MeHgSe to HgSe
fish intake. The higher values of HBVSe, Se/Hg molar ratio, and Se-HBV and direct geochemical or microbial production of stable complexes
(>1) in marine fish underscore their suitability for human consumption (HgSe or MeHgSe) are two ways hypothesized to diminish Hg
without Hg toxicity. Fish caught in this region are generally found to bioavailability to bacteria. In either case, either the MeHg produced is
have Hg levels below the MRL, indicating that they are safe to consume. less bioavailable or less inorganic Hg is available for microbial
However, there are no restrictions on the consumption of marine sea methylation. Experiments using bacterial cultures provide increasing
food in the GoM on the SECI. evidence for the hypothesis that Hg is rendered nonbioavailable for
methylation or absorption by forming inert HgSe complexes in soils and
3.6. Se–Hg interaction and its protective mechanism sediments with high Hg and SeIV concentrations (Gerson et al., 2020).
Extensive research conducted by Gerson et al. (2020), Gochfeld and
Trace amounts of Se are required for normal physiological function Burger (2021), and Zampetti and Brandt (2023) corroborates the hy
in many organisms, including humans. It is a component of the enzyme pothesis that Se provides some protection against Hg toxicity. The pre
glutathione peroxidase (GPx), which protects cells from oxidative ventive effect of mercuric chloride and Se was initially observed in rats
damage by catabolizing hydrogen peroxide and lipid peroxide (Gochfeld fed these diets, which showed lower death rates than rats fed the same
and Burger, 2021). GPx consists of four identical subunits, each of which diets with only mercuric chloride. Specific consequences of Hg
contains an atom of Se. Animals and fish absorb water-soluble Se mol poisoning are reduced by Se, which helps restore antioxidant levels,
ecules quickly through the digestive system (Kumar et al., 2023). The stimulates development, and protects against fatality (Ringuet et al.,
organism converts both organic and inorganic Se molecules into sele 2021). Total Se and Hg are found to exist in a 1:1 M ratio, and the for
nide, which is then integrated into selenocysteine and protein. Con mation of HgSe precipitates in the liver tissues of marine animals points
sumption of Se varies widely around the globe (Ralston et al., 2016). to a possible role for Se in Hg detoxification. Hg and Se co-exposure has
According to research conducted in China’s Se-deficient Keshan Prov additive, greater-than-additive, or synergistic effects on nematodes,
ince, children with low Se levels are at risk for cardiomyopathy (Keshan aquatic invertebrates, fish, birds, and mammals (Gerson et al., 2020). A
protective effect of Se against Hg has also been demonstrated (Copat
et al., 2014). Future research will focus more on questions such as the
Table 6
Principle component analysis (PCA) of Hg and Se in fish.
species-wise variation and bioaccumulation levels of Se and Hg in fish
species, as well as the toxicity of Hg under Se protection, the role of the
Loading factors PC-1 PC-2
Se–Hg complex in vivo, the response of organisms to the Se–Hg complex,
Se 0.263 0.626 and so on (Ghorai et al., 2022; Wu et al., 2023).
Hg − 0.048 0.613
Length 0.605 − 0.134
Weight 0.540 − 0.370 4. Conclusion
Trophic level 0.521 0.279
Eigenvalue 2.071 1.117 The scientific community needs data and information on the Hg, Se,
% Variance 41.42 22.34 Se/Hg molar ratio, and risk–benefit analysis (Se-HBV and HBVse) for
Cumulative variance % 41.42 63.77
commercially significant marine fish. Regarding the safety of consuming
12
U. Arisekar et al. Food Research International 180 (2024) 114086
marine products, they must be taken into account. The concentration of Thamirabarani River, the Western Ghats of South Tamil Nadu. Marine Pollution
Bulletin, 159, Article 111496.
Se found in marine fish demonstrates that they are an excellent source of
Arisekar, U., Shakila, R. J., Shalini, R., Sivaraman, B., Jeyasekaran, G., & Malini, N. A. H.
this essential element. Hg detected in marine fish was determined to be (2021). Heavy metal concentration in reef-associated surface sediments, Hare Island,
below the MRL stipulated by the EC and FSSAI, showing that the fish Gulf of Mannar Marine Biosphere Reserve (southeast coast of India): The first report
caught along the GoM coast were not polluted with Hg and were safe for on pollution load and biological hazard assessment using geochemical normalization
factors and hazard indices. Marine Pollution Bulletin, 162, Article 111838.
human consumption. Se concentrations in marine fish were discovered Arisekar, U., Shakila, R. J., Shalini, R., Jeyasekaran, G., Sivaraman, B., & Surya, T.
in the following order: pelagic > demersal > benthic, with positive (2021). Heavy metal concentrations in the macroalgae, seagrasses, mangroves, and
correlations observed with size (length and weight) and TL. Similarly, crabs collected from the Tuticorin coast (Hare Island), Gulf of Mannar. South India.
Marine Pollution Bulletin, 163, Article 111971.
Hg concentrations in fish were reported in the following order: Arisekar, U., Shakila, R. J., Shalini, R., Jeyasekaran, G., Keerthana, M., Arumugam, N., …
pelagic > benthic > demersal, showing weak links with TL and habitat Perumal, K. (2022). Distribution and ecological risk assessment of heavy metals
and negative correlation with size. Higher Hg concentration was found using geochemical normalization factors in the aquatic sediments. Chemosphere, 294,
Article 133708.
in E. affinis, which was closely related to habitat and TL. The Se/Hg Arisekar, U., Shakila, R. J., Shalini, R., Jeyasekaran, G., Padmavathy, P., Hari, M. S., &
molar ratio and selenium health benefit indexes (Se-HBV and HBVse) Sudhan, C. (2022). Accumulation potential of heavy metals at different growth
suggest that fish caught from this location pose no health risks and stages of Pacific white leg shrimp, Penaeus vannamei farmed along the Southeast
coast of Peninsular India: A report on ecotoxicology and human health risk
provide the preventive effect of Se on Hg toxicity. HRA obtained from assessment. Environmental Research, 212, Article 113105.
marine fish consumption (THQ/HQ1) reveals that it does not pose any Arisekar, U., Shakila, R. J., Shalini, R., Jeyasekaran, G., Arumugam, N., Almansour, A. I.,
carcinogenic risk. However, the THQ and HI values of E. affinis were … Perumal, K. (2022). Bioaccumulation of organochlorine pesticide residues (OCPs)
at different growth stages of pacific white leg shrimp (Penaeus vannamei): First
greater, raising concerns, but their Se/Hg ratio (>1), Se-HBV, and
report on ecotoxicological and human health risk assessment. Chemosphere, 308,
HBVse index of E. affinis revealed positive values, indicating that Se has Article 136459.
a neutralizing effect on Hg. The MRL of Hg in E. affinis was also far lower Arisekar, U., Shalini, R., Sundhar, S., Sangma, S. R., Rathinam, R. B., Albeshr, M. F., …
than the MRL of 1.0 mg/kg established by the EC (2006, 2022) and Sahana, M. D. (2023). De-novo exposure assessment of heavy metals in commercially
important fresh and dried seafood: Safe for human consumption. Environmental
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the relatively high Se-HBV and HBVse and Se/Hg molar ratios (>1) of all Arisekar, U., Shalin, R., Shakila, R. J., Sundhar, S., Iburahim, S. A., & Umamaheshwari, T.
commercially important marine fish suggest that this species may (2024). Trace metals in commercial seafood products (canned, pickled and smoked):
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contain acceptable levels of Se and lower levels of Hg, which may result Article 113969.
in a beneficial health effect for human consumption. Marine fish have Arulkumar, A., Paramasivam, S., & Rajaram, R. (2017). Toxic heavy metals in
the potential to enhance the status of selenium without reaching harmful commercially important food fishes collected from Palk Bay. Southeastern India.
Marine Pollution Bulletin, 119(1), 454–459.
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Declaration of competing interest Cabrini, T. M., Barboza, C. A., Skinner, V. B., Hauser-Davis, R. A., Rocha, R. C.,
Saint’Pierre, T. D., … Cardoso, R. S. (2018). Investigating heavy metal
bioaccumulation by macrofauna species from different feeding guilds from sandy
The authors declare that they have no known competing financial
beaches in Rio de Janeiro, Brazil. Ecotoxicology and Environmental Safety, 162,
interests or personal relationships that could have appeared to influence 655–662.
the work reported in this paper. Cammilleri, G., Galluzzo, F. G., Fazio, F., Pulvirenti, A., Vella, A., Lo Dico, G. M., …
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