Detection of Pollutants from Mollusc Shells

MITITELU Magdalena1#, DUMITRESCU Denisa Elena2#, NICOLESCU Teodor Octavian3#, NEACȘU Sorinel Marius1#, MOROȘAN Elena1#, IONIȚĂ Ana Corina1#, UDEANU Denisa Ioana1#, NICOLESCU Florica4#

1Clinical Laboratory and Food Hygiene Department, Faculty of Pharmacy, ”Carol Davila” University of Medicine and Pharmacy, 6, Traian Vuia Street, 020956, Bucharest (ROMANIA)

2 Organic Chemistry Department, Faculty of Pharmacy, Ovidius University, Constanța (ROMANIA)

3 Organic Chemistry Department, Faculty of Pharmacy, ”Carol Davila” University of Medicine and Pharmacy, 6, Traian Vuia Street, 020956, Bucharest (ROMANIA)

4 Toxicology Department, Faculty of Pharmacy, ”Carol Davila” University of Medicine and Pharmacy, 6, Traian Vuia Street, 020956, Bucharest (ROMANIA)

Authors emails: magdamititelu@yahoo.com, denisadumitrescu@yahoo.com, nicolescu.teodor@gmail.com,  neacsu_23@yahoo.es, morosan_elena@yahoo.com, ionita_ana_corina@yahoo.com,  florica.nicolescu@gmail.com 

#Author Contributions: All authors have equally contributed to the work reported

Abstract

This paper presents aspects regarding some heavy metals (cadmium, lead, copper and zinc) concentration in shells of different molluscs collected from the Romanian Black Sea Coast (Rapana thomasiana, Mytilus galloprovincialis, Mya arenaria, Scapharca). Detection of heavy metals was made using atomic absorption spectrometry.

Keywords: molluscs shells, heavy metals, atomic absorption spectrometry

Introduction

      Mollusks are invertebrates with a soft body, sometimes their bodies protected by a shell or a system composed of two valves (shells). The main classes of this group are gastropods, bivalves and cephalopods. Bivalves are the most famous shells appreciated both for their nutritional value and for the fact that they are used for commercial purposes – the production of pearls, mother-of-pearl, etc [1,2,3]. 

       Bivalves or lamellibranchs are represented by shells, aquatic molluscs protected by a shell formed by two valves, joined by a strong ligament. The shell can be closed and opened by the contraction and relaxation of some muscles. Shells feed by filtering water, aspirating water and filtering feed particles. Shells are the food of other animals as well as humans, and also produce pearls. The process of pearl formation occurs when certain particles (sand, parasites) enter the shell and then the shell coats these particles in mother-of-pearl, thus forming pearls. In some countries, such as Japan, this process is artificially caused by the introduction of particles inside the shells. All bivalves live in water, most in the sea. Some are fixed to rocks, but others hide in the sand and shore. By drawing a stream of water into the shell, they filter food particles and oxygen [4].

      By ingestion of contaminated or polluted food and water the population can be contaminated with heavy metals and organic pollutants. Unfortunately, most of these pollutants are very persistent and non-biodegradable and they can be bio-accumulate through the biologic chains: soil-plant-food and seawater-marine organism-food [5,6,7]. For this reason, accurate monitoring of their concentration plays an important role. Pollutant toxicity is influenced by concentration, nature of pollutant, body resistance and presence of other contaminants [8,9,10,11]. 

      Clinical studies have shown that people who eat fatty fish (salmon, mackerel, mackerel) or white meat (cod, haddock, turbot) and seafood at least once a week reduce their risk of type II diabetes by 25 % [12-17]. The concentration of pollutants in food products is varied, depending of their origin, processing technologies and storage conditions. So, the presence in high amount of organic pollutants and heavy metals in environment represents a potential danger for human health and for environment due to their extreme toxicity [18-25].   

      There are many methods for analysing heavy metals in plants, soils, seawater, biologic or other materials: inductive coupled plasma – atomic emission spectrometry, inductive coupled plasma – mass spectrometry, atomic absorption spectrometry with flame or electrothermal atomization, electrochemically with ultra-microelectrodes, anodic stripping voltammetry [26,27,28]. 

       Concentrations of many organic pollutants are below the detection limits of standard analytical and sampling methods due of the large scale dilution of organic contaminants in the aquatic matrices. For analyse pesticides and polycyclic aromatic hydrocarbons concentrations in water samples is frequently used gas chromatography with specific detection methods such as electron capture detector and HPLC [5,6].

        In this paper is analysed heavy metals concentration (cadmium, lead, copper and zinc) in different mollusc shells (Mytilus galloprovincialis, Rapana thomasiana, Mya arenaria, Scapharca) collected from the Romanian Black Sea Coast. The heavy metals were analysed using atomic absorption spectrometry. 

Methodology

       The mollusc shells (Rapana thomasiana, Mytilus galloprovincialis, Mya arenaria, Scapharca) were collected during August 2019 on the Romanian Black Sea Coast. 

        The shell samples were washed, dried at 105 0C, pulverised and then mineralized by wet digestion method (HNO3– H2SO4) for to analysed the heavy metals concentrations. About 0.5g of each powder of shells sample was pre-digested using 2 mL 65% HNO3 for 24 hours at room temperature, then 2 mL of 98% H2SO4 were added and the mixture was digested in a VELP DK6 heating digester. After cooling, the solution was made up to 25 mL of deionised water. The resultant solutions were analysed with an atomic absorption spectrophotometer GBC-AVANTA (air / acetylene flame) for to determine the heavy metals concentration: Cd (λ = 228.8 nm), Cu (λ = 324.7 nm), Zn (λ = 213.9 nm) and Pb (λ = 217 nm). Two replicate determinations were done for each solution. All used reagents were of analytical reagent grade (Merck). The data were statistical processing by t student test [29].

Results 

     The heavy metals concentrations in the samples analysed are presented in the figures below (fig. 1-4):

μg/g in dry sampl

Fig. 1  Concentration of Zn in the analysed samples

μg/g in dry sample 

Fig. 2 Concentration of Cu in the analysed samples

 μg/g in dry sample 

Fig. 3 Concentration of Cd in the analysed samples

     μg/g in dry sample 

Fig. 4  Concentration of Pb in the analysed samples

According  to Fig. 1 we remark that the highest concentrations of Zn are detected in the Mytilus (22.98 μg/g) and Rapana (16.81 μg/g) samples. The lowest concentration of zinc was recorded in Scapharca sample (2.86 μg/g).

As we can see in the figure 2 in the Rapana sample we have detected the lower concentration in Cu (5.88μg/g) and the highest cooper concentration was detected in Mytilus sample (10.61 μg/g). In the shells samples of Rapana we have detected the high concentration in Cd (0.98 μg/g) according to figure 3.

   From figure 4 we remark that the shells of Scapharca have presented the lower concentration in Pb (3.11 μg/g) but in Mya arenaria samples it was detected the highest concentration in Pb (9.93 μg/g).

Conclusions

      The concentration analisys of heavy metals from the Black Sea molluscs presents a major importance because in the seawater are discharged the most effluents and molluscs have bioindicator properties. These are biofilter organisms which retain small particles from seawater, so the presence of pollutants in molluscs indicate a contamination of marine environmental. 

     The heavy metals concentrations in the samples of molluscs shells analyzed are generally presented high values and their presence indicates a high degree of pollution and also permits us to identify the major contamination sources. We have detected the highest concentrations Cd in the shells samples of Rapana and Pb in the Mya samples. 

      We also remark that the shells samples of Scapharca have presented the lower concentration in heavy metals.

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