Microplastics in the Mediterranean Sea: Impacts on Marine Environment 3031304802, 9783031304804

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SpringerBriefs in Environmental Science Monique Mancuso · Nunziatina Porcino · Julian Blasco · Teresa Romeo · Serena Savoca · Nunziacarla Spanò · Teresa Bottari

Microplastics in the Mediterranean Sea Impacts on Marine Environment

SpringerBriefs in Environmental Science

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Monique Mancuso • Nunziatina Porcino Julian Blasco • Teresa Romeo • Serena Savoca Nunziacarla Spanò • Teresa Bottari

Microplastics in the Mediterranean Sea Impacts on Marine Environment

Monique Mancuso Institute for Marine Biological Resources and Biotechnology (IRBIM) – CNR Messina, Italy

Nunziatina Porcino Institute for Marine Biological Resources and Biotechnology (IRBIM) – CNR Messina, Italy

Julian Blasco Departamento Ecología y Gestión Costera Consejo Superior De Investigaciones Científicas Instituto de Ciencias Marinas de Andalucía Puerto Real, Cádiz, Spain

Teresa Romeo Department of Integrative Marine Ecology (EMI) Stazione Zoologica Anton Dohrn - National Institute of Biology, Ecology and Marine Biotechnology Messina, Italy

Serena Savoca Department of Biomedical, Dental and Morphological and Functional Imaging University of Messina Messina, Italy Teresa Bottari CNR Institute for Marine Biological Resources and Biotechnology (IRBIM) Messina, Italy

Nunziacarla Spanò Department of Biomedical, Dental and Morphological and Functional Imaging Università di Messina Messina, Italy

ISSN 2191-5547     ISSN 2191-5555 (electronic) SpringerBriefs in Environmental Science ISBN 978-3-031-30480-4    ISBN 978-3-031-30481-1 (eBook) https://doi.org/10.1007/978-3-031-30481-1 © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 This work is subject to copyright. All rights are solely and exclusively licensed by the Publisher, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilms or in any other physical way, and transmission or information storage and retrieval, electronic adaptation, computer software, or by similar or dissimilar methodology now known or hereafter developed. The use of general descriptive names, registered names, trademarks, service marks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. The publisher, the authors, and the editors are safe to assume that the advice and information in this book are believed to be true and accurate at the date of publication. Neither the publisher nor the authors or the editors give a warranty, expressed or implied, with respect to the material contained herein or for any errors or omissions that may have been made. The publisher remains neutral with regard to jurisdictional claims in published maps and institutional affiliations. This Springer imprint is published by the registered company Springer Nature Switzerland AG The registered company address is: Gewerbestrasse 11, 6330 Cham, Switzerland

Preface

In modern life and every day, plastic has become indispensable; in fact, it is enough to look around us to see how plastic is constantly present in our lives. From everyday objects (brushes, combs, toothbrushes, headbands, elastic bands, lunch boxes, clothes, etc.) up to the big industries, plastic has taken over so much so that we talk more and more about the era of plastic. In the 1950s, the boom of plastic as the “material of the future” brought about significant changes in the lifestyle of human beings. This material is well suited to the most varied uses, and this led to a large production of plastics. However, on the other hand, unfortunately, over time we have discovered that plastic is a material that is difficult to dispose of and very refractory to biodegrade; in fact, our oceans and seas have begun to accumulate plastics. Therefore, nowadays, in our “modern life,” plastics are ubiquitous! The huge number of plastics that is dumped into our oceans every year, and that recently has increased exponentially, is causing several problems; for example, in some places, the presence of plastic in the water makes it impossible to dive; or in other places, the beaches are so full of plastic litter that it is impossible to see the sand! Several plastic islands are floating in the middle of the ocean, all of which made us understand that plastic litter is causing significant harm to the aquatic environment. Although, as we said above, plastics are refractory to biodegradation, some plastics that reach the seawater are degraded by sunlight and become brittle and fracture, while others are thrown around by waves, ultimately breaking apart into countless tiny colorful pieces, termed microplastics (MPs) and nanoplastics (NPs); this latter is still unknown in Mediterranean marine ecosystems. Some of these tiny pieces of plastic float on the surface water, while others sink to the seabed or are carried along by currents, meandering and swirling as they go. Moreover, some industries create microplastics as tiny spheres for use in cosmetics and personal care products. These microscopic plastics once arrived in the sea can mistake for food by marine fauna. Moreover, some toxic chemicals that are present in the sea can be absorbed by MPs and NPs and can concentrate to levels up to one million times higher than that of the surrounding water. If these contaminated MPs and NPs are subsequently consumed by an organism, the contaminants may leach off the v

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Preface

microplastics and deliver a dose of toxic chemicals into that organism. If this contaminated organism is then consumed by a predator, the toxic chemicals are also consumed. In the process of biomagnification, the toxic chemicals may potentially be transferred to successively higher levels in the food chain, with organisms at higher levels tending to accumulate a substantially greater concentration of toxic chemicals in their tissues. In addition, several authors reported that some kinds of MPs and the NPs can be absorbed by the gastrointestinal (GI) tract and can pass into other body districts, such as muscle, liver, blood, etc. Messina, Italy  Monique Mancuso Messina, Italy  Nunziatina Porcino Puerto Real, Cádiz, Spain  Julian Blasco Messina, Italy  Teresa Romeo Milazzo, ME, Italy Messina, Italy  Serena Savoca Messina, Italy  Nunziacarla Spanò Messina, Italy  Teresa Bottari

Purpose of the Book

The purpose of this book is to bring together the latest research carried out on pollution by microplastics (MPs) in the Mediterranean Sea. As is known, the Mediterranean Sea is a semi-closed basin with peculiar circulation characteristics; recently, it was seen that the set of plastics in the sea is increasing visibly. The main topics will be related both to the source of pollution, to the distribution along the coasts of the Mediterranean countries, and to the impact that these microscopic plastics have on native flora and fauna as well as on farmed organisms. In addition, we will discuss the latest techniques used by scientists to isolate and characterize microplastics and the identification of toxic substances that can attach to them. Finally, a chapter will cover the possible future consequences and the possible solution to the problem. This book will therefore give us an overview of what was happening in recent years in the Mediterranean Sea. The book will be used not only for scientists but also for professionals and students of biology or related subjects. This is the first book dedicated exclusively to microplastics in the Mediterranean Sea. Reading this book we expect that people gain a greater awareness of these implications and help bring the world’s attention to microplastics pollutants in the Mediterranean Sea.

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Contents

1

 The Mediterranean Sea a Marine Ecosystem in Risk��������������������������    1 1.1 Introduction��������������������������������������������������������������������������������������    1 1.2 Microplastic Pollution: The Mediterranean Sea ������������������������������    3 1.3 Source of Microplastic Pollution in the Mediterranean Sea ������������    4 1.4 The Mediterranean an Ecosystem in Risk����������������������������������������    6 1.5 Policies to Reduce Microplastic Pollution in the Mediterranean Region ����������������������������������������������������������������������������������������������    6 1.6 Conclusion����������������������������������������������������������������������������������������    8 References��������������������������������������������������������������������������������������������������    8

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 Microplastics in the Mediterranean Biota ��������������������������������������������   13 2.1 Introduction��������������������������������������������������������������������������������������   13 2.2 Microplastics and Posidonia oceanica Egagropyls��������������������������   15 2.3 Microplastics and Marine Invertebrates��������������������������������������������   16 2.3.1 Mediterranean Zooplankton��������������������������������������������������   16 2.3.2 Mediterranean Jellyfish��������������������������������������������������������   17 2.3.3 Mediterranean Molluscs�������������������������������������������������������   17 2.3.4 Mediterranean Seaworms������������������������������������������������������   19 2.3.5 Mediterranean Crustaceans��������������������������������������������������   19 2.3.6 Mediterranean Echinoderms ������������������������������������������������   21 2.4 Microplastics and Mediterranean Fish����������������������������������������������   23 2.4.1 Mediterranean Elasmobranchs����������������������������������������������   23 2.4.2 Mediterranean Osteichthyes�������������������������������������������������   23 2.5 General Comment on Microplastics in Elasmobranchs and Fish ����   41 2.6 Mediterranean Turtles ����������������������������������������������������������������������   48 2.7 Mediterranean Marine Mammals������������������������������������������������������   48 2.8 Effects of Microplastics in the Mediterranean Marine Biota������������   50 2.9 Microplastics Extraction and Characterization Methods������������������   52 2.10 Conclusions��������������������������������������������������������������������������������������   57 References��������������������������������������������������������������������������������������������������   58

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 Microplastics in Mediterranean Seawater��������������������������������������������   67 3.1 Introduction��������������������������������������������������������������������������������������   67 3.2 Horizontal Transport of Microplastics in the Marine Environment ��������������������������������������������������������������   69 3.3 Vertical Transport and Settling of Microplastics in the Marine Environment ��������������������������������������������������������������   69 3.4 Concentration and Polymeric Composition of Floating Microplastics in the Mediterranean Sea ������������������������   70 3.5 Concentration and Polymeric Composition of Microplastics in the Water Column of the Mediterranean Sea��������������������������������   72 3.6 Effect of Sampling Methods on Microplastics Estimation ��������������   74 3.6.1 Surface Waters����������������������������������������������������������������������   74 3.6.2 Water Column ����������������������������������������������������������������������   75 3.6.3 Conclusion and Future Research Recommendations������������   76 References��������������������������������������������������������������������������������������������������   78

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 Microplastics in Mediterranean Sediments������������������������������������������   83 4.1 Introduction��������������������������������������������������������������������������������������   83 4.2 Samples Collection and Extraction��������������������������������������������������   85 4.3 Microplastics Quantification and Characterization��������������������������   85 4.4 Microplastics in the Mediterranean Basin����������������������������������������   85 4.5 Conclusion����������������������������������������������������������������������������������������   94 References��������������������������������������������������������������������������������������������������   94

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Toxic Substances on Microplastics and Risk Assessment of Microplastics Pollution in the Mediterranean Sea ��������������������������   97 5.1 Introduction��������������������������������������������������������������������������������������   97 5.2 Chemicals Associated with Microplastics����������������������������������������   99 5.2.1 Inorganic Toxics in the Mediterranean Sea: Heavy Metals������������������������������������������������������������������������   99 5.2.2 Organic Toxics in the Mediterranean Sea ����������������������������  100 5.3 Risks to Environment and Human Health����������������������������������������  103 5.4 Conclusion����������������������������������������������������������������������������������������  104 References��������������������������������������������������������������������������������������������������  104

Abbreviations

ABS Acrylonitrile-butadiene-styrene copolymer CA Cellulose acetate Ce Cellophane CL Cellulose CR Polychloroprene CTA Cellulose triacetate EPDM Ethylene-propylene copolymer EPR Ethylene propylene rubber EPS Expanded polystyrene EVA Ethylene-vinyl acetate HDPE High-density polyethylene Kraton g Triblock copolymer LDPE Low-density polyethylene MPA Marine-protected area MPs Microplastics N Neoprene NBR Nitrile butadiene rubber NFC Natural fiber cotton NFW Natural fiber wool NY Nylon NY66 Nylon 66 PA Polyamide PAC Polyacrylate PAN Polyacrylonitrile PBT Polybutylene terephthalate PC Polycarbonate PE Polyethylene PEP Poly(ethylene-propylene) PES Polyether sulfone PET Polyethylene terephthalate

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PEVA Polyethylene vinyl acetate PIB Polyisobutylene rubber PL Polyester PMA Poly(methyl methacrylate) PO Polyacrylate polyester PP Polypropylene PS Polystyrene PTFE Polytetrafluoroethylene PU Polyurethane PVC Polyvinyl chloride PVDF Polyvinylidene fluoride RA Rayon SAN Styrene acrylonitrile resin SBR Styrene butadiene TPU Thermoplastic PU Polyurethane U Unidentified VI Viscose

Abbreviations

Chapter 1

The Mediterranean Sea a Marine Ecosystem in Risk

Abstract  The Mediterranean Sea is highly populated and is one of the busiest commercial traffic seas, and it is heavily impacted by MPs, and for this reason, was recognized as a target hotspot of the world as microplastics concentration. Several plastic types are found in the Mediterranean Sea, their polymeric characteristics play an important role in the interactions between these plastic particles and other organic matter in the sea. To combat this pollution, several Mediterranean countries are adopting a series of important regulations and policies, to monitor, control, manage, and overall prevent and reduce microplastics pollution. Keywords  Microplastics pollution · Sources · Policies · Mediterranean Sea

1.1 Introduction This chapter aims to give a general overview of microplastic (MP) pollution in the Mediterranean Sea, and moreover, to give a general book presentation. The book presents a collection of all found papers related to MPs in the Mediterranean Sea. Chapter 2 focus on the MPs in the Mediterranean biota and the related effects, while Chaps. 3 and 4 are about the presence of MPs in seawater and marine Mediterranean sediments. Finally, the last chapter focuses on the toxic chemicals associated with the MPs and their relationship with the biota and humans. Since the creation of the first synthetic polymer, the ‘Bakelite’, a phenol-­ formaldehyde thermoset in 1907, plastic has become increasingly present in our lives. Plastic was created to replace raw materials which were beginning to become rare and, consequently, very expensive, such as silk and ivory. And, over time, it has become indispensable for man (Davis 2015). At the end of the World War II, the annual plastics production increased exponentially, until it reached 5 million tons in the 1950s (Andrady and Neal 2009). In the last decades, plastic pollution increased exponentially in all environments. Plastic production increased from 30 million tons in 1988 up to 8300 million tons (Walker 2021), of which 6300 million tons became © The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. Mancuso et al., Microplastics in the Mediterranean Sea, SpringerBriefs in Environmental Science, https://doi.org/10.1007/978-3-031-30481-1_1

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solid waste, 10% is recycled, while 79% enter directly into terrestrial and aquatic environments (Tejaswini et al. 2022). Plastic in natural environments leads to widespread contamination of the atmosphere (Xu et al. 2020), soil, and water (Su et al. 2022). Borrelle et al. (2020) estimated that 23 million tons of plastic waste have entered the oceans. It is estimated that 93–268 ktons of MPs are currently accumulating within the oceans (Boucher and Friot 2017), and as defined by several authors, due to the magnitude and effects of this global ocean contamination, the present period is being referred to as the ‘plasticene’ (Reed 2015). Plastics in aquatic environments are transformed into tiny fragments, classified as macroplastics (> 25 mm), mesoplastics (5–25 mm), microplastics (MPs) (< 5 mm), and nanoplastics (NPs) (< 1 mm) (Galgani et al. 2013). The MPs comprise a very heterogeneous group of particles that vary in size, shape, color, chemical composition, density, and other characteristics (Boucher and Friot 2017). They can be released directly as tiny particles so-called primary MPs or can be derived from the gradual weathering or abrasion of larger plastic material into smaller fragments due to mechanical, photolytic, and/or chemical degradation processes in the marine environment (secondary MPs) (Mathalon and Hill 2014). Most MPs in the marine environment are secondary (Ivar do Sul and Costa 2014; Duis and Coors 2016). The primary MPs are intentionally produced at a microscopic scale (Costa et al. 2010) and usually are used in facial cleansers, toothpaste, and hand scrubs (Derraik 2002). Moreover, they are found in paint and city dust (Boucher and Friot 2017), and may be originated during the manufacture and maintenance of larger plastics by abrasion, such as by the erosion of tyres and by the laundering and wearing of textiles (microfibers). The main source of microfibers in the marine environments is textile products (Carr 2017; Gavigan et al. 2020). Every year synthetic textiles are responsible for the discharge of about half a million tonnes of MPs into the seawater (Manshoven et al. 2022). Natural and semisynthetic microfibers can persist in the marine environments for decades in relation to their chemical composition and to the environmental factors. Moreover, the degradation of natural and semisynthetic fibers involves the release of toxics adsorbed to the surface in the environment as industrial dyes and additives (Remy et al. 2015). The secondary MPs are generated by the breakdown of larger plastics (Auta et al. 2017). The fragmentation is slow and is caused by a combination of mechanical forces such as waves and/or photochemical processes triggered by sunlight mainly through prolonged exposure to solar UV radiation, moreover, the reduction is due to biodegradation acted by living organisms (usually microbes) (Barnes et al. 2009; Andrady 2011; Mathalon and Hill 2014).

1.2  Microplastic Pollution: The Mediterranean Sea

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1.2 Microplastic Pollution: The Mediterranean Sea The Mediterranean Sea is a semi-closed basin and represents a biodiversity hotspot at a global scale thanks to the high level of endemism (Bazairi et al. 2010). The Mediterranean has limited exchanges with the Atlantic Ocean (Tanhua et al. 2013), consisting of two basins of approximately equal size (the Western basin bordered by Spain, France, Italy, Tunisia, Algeria, and Morocco, and including the Adriatic Sea, and the Eastern basin bordered by Greece, Turkey, the Levant, Egypt, and Libya) (Boucher and Billard 2020). The Mediterranean Sea is one of the busiest and the most strategic navigational corridors in the world. It presents high urban and industrial concentrations on the coast and around the rivers, which make it prone to the accumulation of significant amounts of marine litter (Boucher and Billard 2020; Cózar et al. 2015; Llorca et al. 2020; Papadimitriu and Allinson 2022). In fact, the Mediterranean Sea is the sixth great accumulation area for marine litter (Cózar et al. 2014; Gesamp 2016). The highest concentrations of plastic were detected near the most populated and urbanized centers, with the areas most impacted represented by the Cilician Sea, the Catalan Sea, the NW Adriatic Sea, and the Gulf of Lion. Moreover, it has also been detected the presence of local hotspots for plastics concentration. These are relatively small areas near the pollution sources with a limited water circulation (e.g., the Saronic Gulf in the Aegean Sea, the Buna-Bojana plume in the Adriatic, the Gulf of Naples in the Tyrrhenian Sea, the Malaga Bay and the Gulf of Arzew in the Alboran Sea, the Gulf of Tunis, and the Abu Qir Bay) (Liubartseva et al. 2018). This accumulation (between 1000 and 3000 tons) (Cózar et al. 2015) is also due to the hydrodynamics of this semi-enclosed basin. Particularly, in the Mediterranean Sea there is a surface inflow of fresh and warm Atlantic water, with significant plastic inputs, and limited deep outflow of relatively salty and cold Mediterranean water (Béranger et al. 2010). As reported by Cózar et al. (2015) this hydrodynamic model suggests that a proportion of the plastic pollution may originate outside the basin, and defines the Mediterranean Sea as a sink for Atlantic floating plastic pollution. The effects of the intense human activities, added to other factors acting at a global scale (such as global warming and ocean acidification), have led to massive habitat deterioration and a worrying increase in pollution. Among the different pollutants, plastics and microplastics are currently causing major concern to the scientific community, due to their very high concentration (one of the largest in the world) on the surface and their widely reported presence at all the depths in almost the entire basin (Suaria et al. 2016). Moreover, the organisms inhabiting the Mediterranean Sea are not immune to their contamination, as highlighted by a large amount of literature showing the presence of plastic in the stomach contents of many species from different marine domains and trophic levels. Concerning the plastic inputs in the Mediterranean Sea, part of the floating plastics can come from the Atlantic Ocean, as suggested by the hydrodynamic patterns of the basin (Soto-Navarro et al. 2010). However, most of the plastic pollution is

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strictly related to a large number of rivers (e.g., Po, Nile, Rhone) which, passing through densely populated and urbanized areas, flow into the basin carrying many pollutants and debris (Lebreton et al. 2012; Lechner et al. 2014; Liubartseva et al. 2018; Prevenios et al. 2018). The Mediterranean Sea is also characterized by a large presence of plastic debris on the seafloor at different depths, with accumulation zones reported in many different areas (e.g., French Mediterranean coast, Tyrrhenian Sea, Eastern Mediterranean, Cilician Coast, Spanish continental shelf, Sardinian coast) (Angiolillo et al. 2015; Cau et al. 2017; Galgani et al. 2000; García-Rivera et al. 2017; Pierdomenico et al. 2020; Tubau et al. 2015; Vlachogianni et al. 2018).

1.3 Source of Microplastic Pollution in the Mediterranean Sea The Mediterranean basin, connected to the Atlantic Ocean by the Strait of Gibraltar, receives water from several highly populated catchment areas such as the Nile, Rhône, and Po. The total annual plastic input is equal to 100,000 tons, 50% derives from various terrestrial sources, 30% comes from rivers, and 20% comes from maritime activities Cincinelli et al. (2019). Marine plastic debris may be classified as land-based or sea-based, depending on the way they reach the marine environment. The land-based debris comes from sewage streams, rivers, stormwater runoffs, and wind currents, and are attributed to the 21 Nations bordering the Mediterranean basin, whose come from different daily domestic, industrial, commercial, and tourist activities. The sea-based sources of plastic waste are due to tourist/merchant ships, commercial, and fishing businesses, military fleets, offshore activities (oil and gas stations), and aquaculture sites. The development of the plastic industry, through the production of synthetic polymers, has strongly influenced the nature of plastic debris with the replacement of natural materials with those of a synthetic or semi-synthetic nature (cheaper, more durable, and easier to handle) allowing advancements in different sectors, such as in aquaculture (Valdemarsen 2001). According to the data published by UNEP/MAP (2015), the main coastal countries dumping a significant amount of plastic in the Mediterranean are Turkey (144 tons/day), Spain (126 tons/day), Italy (90 tons/day), France (66 tons/day), and Egypt (77 tons/day). Alessi and Di Carlo (2018) noted that the Mediterranean basin produces about 208–760 kg of solid waste per capita per year and, as reported by Galgani et al. (2014), it would seem that tourism activities are one of the major contributors to this increase in marine litter. Here are reported the contribution of some of the coastal countries to microplastic pollution in the Mediterranean. Spain consumes 3.84 million tons of plastic

1.3  Source of Microplastic Pollution in the Mediterranean Sea

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items/year, which represents ~10% of single-use plastic consumed across Europe. It was estimated the use of plastic bottles (3500 million), plastic cups (1500 million), plastic straws (5000 million), and single-use containers (207 million), of which only 35–38% of plastic is recycled (Alessi et al. 2018). Because Italy consumes about 2.1 million tons/year of single-use plastic, the Italian population was indicated as one of the “supreme consumers” of single-use plastic, reaching 70% across Europe. Moreover, due to the limited recycling process (40%) the dumping into the sea of plastic waste is massive (Alessi and Di Carlo 2018). Greece consumes ~6 million tons of plastic items/year and only 20% of these are recycled. France is one of the top three consumers of plastic in Europe, with about 2–4 million tons of plastic items. Plastic bags and bottles are the main ones responsible for MPs pollution in the Mediterranean, however, the low recycling of plastic waste (only 21%) contributes to worsening the already dramatic rate of pollution, resulting in the disposal of an important portion of plastic waste in the Mediterranean basin (Alessi and Di Carlo 2018). Croatia used ~54,744 tons of packaged plastic and polystyrene products only in 2016. The main debris finds out in the Croatian seas and coasts are plastic bottles, plastic straws, and plastic caps. Moreover, only 50% of plastic debris is recycled (Jovičić et al. 2017). According to a report published in 2017, Turkey used about 1.24 million tons of plastic in 2015. Also in this country, only 35–40% of plastic waste is recycled (Gündoğdu and Çevik 2017). Several MPs shapes are reported in the Mediterranean Basin, such as polyester foam, fibres from textiles, filaments of fishing gears, fragments, films, and spheres, having different chemical compositions (Marrone et al. 2021). For what concerns polymeric abundance, de Haan et al. (2019) found that polyethylene, polystyrene, polyester, and polypropylene were the most abundant in the Mediterranean Sea. Polyethylene is the most abundant type of polymer in the Mediterranean Sea (54.5%) (de Haan et al. 2019), the primary use of this polymer is for packaging and the global production is about 85 million tons every year (Bayo et al. 2018). Polyethylene exists in two forms high-density polyethylene (HDPE) and low-­ density polyethylene (LDPE). The first one is a polymer composed of ethylene units with high acid resistance property is rigid, colorless and lightweight, and is used in plastic containers, motor oil, detergent, etc. The second one has higher flexibility than HDPE and it is used as a constituent in supermarket plastic bags and used as a wrap for food products (Bayo et al. 2018). Other dominant MPs are polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS), ethylene-vinyl acetate (EVA), polyvinyl chloride (PVC), and polyurethane (PUR). Plastics with a density lower than seawater (1.02–1.03  g  mL−1) such as Low-­ density PolyEthylene (LDPE) (0.89–0.94  g  mL−1), High-Density PolyEthylene HDPE (0.94–0.96 g mL−1), Polypropylene (PP) (0.85–0.83 g mL−1), tend to float on the sea surface (Suaria and Aliani 2014) or to stay in suspension in the water column (Fossi et  al. 2012). While polymers with a higher density, such as polyethylene terephthalate (PET) (1.29–1.40  g  mL−1) and Poly(vinyl chloride) (PVC) (1.30–1.58 g mL−1) tend to sink and accumulate in sediments (Woodall et al. 2014;

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Woodall et al. 2015) (Epa 1992). However, over a timescale of weeks to months, MPs with a lower density, may increase their density because of fouling by organisms, such as prokaryotes, eukaryotes and invertebrates, and, once the density exceeds that of seawater, they sink in the seabed (Lobelle and Cunliffe 2011; Van Cauwenberghe et al. 2013). Therefore, the seafloor sediments are the major sink of MPs (Barnes et al. 2009; Galgani et al. 1995; Martellini et al. 2018). Reinold et al. (2021) reported that particle amounts are significantly higher in sediments than in seawater. Moreover, the de-fouling process, due to the foraging of foulants by organisms or other processes, can cause a decrease in the density and the resuspension of the plastic debris on the surface (Song and Andrady 1991). On the contrary, plastics that float on the sea surface wash up on the shoreline and on the beaches.

1.4 The Mediterranean an Ecosystem in Risk The Mediterranean is densely populated and thus there is a high human pressure, this, combined with the limited outflow of surface waters, results in a particularly high residence time of surface water (Cózar et  al. 2015; Lacombe et  al. 1981). Moreover, the Mediterranean Sea is considered a hot spot for biodiversity (Bianchi and Morri 2000). The Mediterranean Sea contains high loads of plastics compared to other regional seas (Compa et al. 2019; Cózar et al. 2015) and for these reasons is considered a hot spot for plastic pollution (Lebreton et al. 2012; Van Sebille et al. 2015). Solomon et al. (2000) developed a probabilistic risk assessment that combines a probability distribution for in situ concentrations with a probability distribution for ecotoxicological data. According to Compa et al. (2019), and Cózar et al. (2015), Everaert et al. (2020) using this new environmental risk approach, revealed that the Mediterranean Sea is a hotspot of marine microplastic risks and this phenomenon will be more pronounced in future decades.

1.5 Policies to Reduce Microplastic Pollution in the Mediterranean Region The studies carried out about the MPs pollution in the Mediterranean Sea and its fate, have carried great alarm, therefore, for some years some countries bordering the Mediterranean Sea were promulgating laws to combat MPs pollution through actions aimed at the mitigation and ban of plastic products together with correct use of the separate waste collection. Several campaigns and legislative policies were formulated to reduce the problem of plastic pollution in the marine ecosystem of the Mediterranean basin.

1.5  Policies to Reduce Microplastic Pollution in the Mediterranean Region

7

Recently, a campaign for the elimination of primary sources of plastic litter and of single-use plastic by the end of 2022 was launched by the United Nations Environment Organization. Li et al. (2018) reported that in Europe, different legislative policies were formulated for all the Member States to monitor the MPs pollution. Gago et al. (2018), highlighted that inside the program Horizon 2020 there is an important initiative to reduce the plastic from the ecosystems. And, in October 2020, the European Parliament prohibited single-use plastics from 2021. Various Mediterranean countries are adopting policies to reduce the threat of environmental plastic pollution (Sharma et al. 2021). The first country was France that in 2016, approved a plan with the aim of ban of single-use plastics. Moreover, was initiate the ban of plastic bags with the aim of achieving the complete ban by the end of 2020 (Bayo et  al. 2018). In addition, France plans to get 100% of recycled plastics by the end of 2025. In Italy, in 2017, plastic bags were completely banned from commercial practices and a tax of 1–3 cents per plastic bag was imposed. In addition, territorial initiatives have also been taken along the Italian territory, for example in 2016, the Tremiti Islands approved a law related to the ban on disposable plastics. Moreover, a fine of 500 euros was foreseen for those who do not respect the law (Bayo et al. 2018). Finally, Alessi and Di Carlo (2018) reported that in early 2020, the use of microbeads and microplastic in domestic products was totally banned. In Greece, the first environmental law on the restriction of plastic bags was promulgated in 2018, and a tax of 4 cents per plastic bag was imposed; in 2019 the tax increased to 7 cents per plastic bag (Bayo et al. 2018). Ekathimerini (2020) reported that the use of this measure reduced the usage of single-use plastic bags (80–85%). In addition, Alessi and Di Carlo (2018) reported the National Solid Waste Strategy and National Strategic Solid Waste Prevention Programme posed the target to reach in 2020 70% of recycled plastic materials. Croatia adopted the Marine and Coastal Management Strategy to address the problem of marine litter. The program includes the protection, preservation, and restoration of marine and coastal ecosystems. Ramieri et al. (2019) highlighted that this policy point to the reduction of plastic pollution and to the preservation of marine protected areas. In addition, several policies were formulated for a new way to preserve food, trying to focus on new ideas on packaging recycling, and reusing. Furthermore, Croatia has improved its plastic waste management system and by 2022, the state has set new targets for a well-established marine waste management system (Alessi and Di Carlo 2018). In Spain, the Royal Decree 293/2018, was born to counteract plastic bag consumption and to dispersion in the environment (Sharma et al. 2021). Regarding African countries bordering the Mediterranean Sea, only Egypt has adopted measures to combat plastics pollution. In 2017, the Ministry of Environment launched the National Initiative on Reduction of Plastic Bags Consumption. This program aimed to reduce plastic bag usage at the commercial level, formulate policies for the reduction of single-use plastics, and to encourage people versus eco-­ friendly alternatives.

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1.6 Conclusion Studies on microplastic pollution in the Mediterranean have shown that this peculiar environment together with its inhabitants is strongly threatened. Based on these information, Sharma et  al. (2021) proposed to adopt urgent actions in the industrial sector, and also to ban completely the use of single-use plastic products. Sharma et al. (2021) suggested re-designing the infrastructure for all production processes that allow the utilization of recycled plastic and all the eco-friendly alternatives. However, although the idea is the right one, if there is no aid from the Governments, the industries will not be able to implement it due to the high management and renewal costs. Furthermore, with the current world crisis linked to the war in Ukraine, the costs of raw materials, and production have increased greatly and therefore at the moment any modernization seems impossible. While it is easier to act upon the tourism industry restricting the utilization of all single-use plastic articles, and must encourage the use of biodegradable resources. Unfortunately, the road to combat this type of pollution is long, and full of pitfalls and only if all the Mediterranean countries adopt a common strategy will it be possible to face this great problem and try to defeat it.

References Alessi E, Di Carlo G (2018) Out of the plastic trap: saving the Mediterranean from plastic pollution. Rome, Italy Alessi E, Di Carlo G, Campogianni S, Başgül Di Carlo E, Jeffries B (2018) Out of the plastic trap: Saving the Mediterranean from plastic pollution. World Wide Fund for Nature, pp 1–28 Andrady AL (2011) Microplastics in the marine environment. Mar Pollut Bull 62:1596–1605. https://doi.org/10.1016/j.marpolbul.2011.05.030 Andrady AL, Neal MA (2009) Applications and societal benefits of plastics. Philos Trans R Soc B Biol Sci 364:1977–1984. https://doi.org/10.1098/rstb.2008.0304 Angiolillo M, di Lorenzo B, Farcomeni A, Bo M, Bavestrello G, Santangelo G, Cau A, Mastascusa V, Cau A, Sacco F (2015) Distribution and assessment of marine debris in the deep Tyrrhenian Sea (NW Mediterranean Sea, Italy). Mar Pollut Bull 92:149–159 Auta HS, Emenike CU, Fauziah SH (2017) Distribution and importance of microplastics in the marine environment: a review of the sources, fate, effects, and potential solutions. Environ Int 102:165–176 Barnes DKA, Galgani F, Thompson RC, Barlaz M (2009) Accumulation and fragmentation of plastic debris in global environments. Philos Trans R Soc B Biol Sci 364:1985–1998. https:// doi.org/10.1098/rstb.2008.0205 Bayo J, Olmos S, López-Castellanos J et al (2018) Non-polymeric chemicals or additives associated with microplastic particulate fraction in a treated urban effluent. WIT Trans Built Environ 179:303–314 Bazairi H, Ben Haj S, Boero F, Cebrian D, De Juan S, Limam A, Lleonart J, Torchia G, Rais C (2010) The Mediterranean Sea Biodiversity: state of the ecosystems, pressures, impacts and future priorities. UNEP Tunis 297:1–100

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Chapter 2

Microplastics in the Mediterranean Biota

Abstract  Microplastics pollution in seawater is a big threat all over the world. This chapter focused on the study of microplastics (MPs) in the marine Mediterranean biota, on the possible impacts, and the effects that this type of pollution entails on the marine biota. We collected all the articles published to date on this topic and compared them in order to understand the extent the MPs pollution in the Mediterranean Sea, try to understand which are the most impacted areas, and which regions still have of the gaps. Methods of isolation and identification of MPs are also discussed. Keywords  Microplastics pollution · Marine biota · Effects · Mediterranean Sea

2.1 Introduction Microplastics (MPs) are strongly present in the Mediterranean Sea causing various types of problems for the marine biota (Mancuso et al. 2021). For this reason, MPs represent a growing threat to marine ecosystems in the Mediterranean Sea (Cincinelli et al. 2019) which is considered a hotspot for marine biodiversity (Coll et al. 2010). In the Mediterranean Sea, plastic pollution reached alarming levels; this basin is considered, in fact, the sixth great accumulation area for marine litter (Cózar et al. 2014; GESAMP 2016). Several studies shown that all compartments of the Mediterranean Sea (water, sediment, and biota) are polluted by MPs. Moreover, MPs distribution and composition are heterogeneous between two sub-basins (Western and Eastern Mediterranean Sea basins) and among the different geographical sub-area of the Mediterranean (GSAs-GFCM 2009) (Table 2.1). The presence of MPs was detected in several marine Mediterranean species such  as invertebrates, fish, turtles, and mammals (Lusher et  al. 2017; Cau et  al. 2019; Collard et al. 2017; Mancuso 2019; Biagi et al. 2021; Mancuso et al. 2021).

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. Mancuso et al., Microplastics in the Mediterranean Sea, SpringerBriefs in Environmental Science, https://doi.org/10.1007/978-3-031-30481-1_2

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Table 2.1  List of the geographical subareas (GSAs) investigated for MPs ingestion in marine biota GSA 1 2 3 4 5 6 7 8 9 10 11.1 11.2 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30

Site Northern Alboran Sea Alboran Island Southern Alboran Sea Algeria Balearic Islands Northern Spain Gulf of Lion Corsica Ligurian, Northern Tyrrhenian Sea Southern and Central Tyrrhenian Sea Western Sardinia Eastern Sardinia Northern Tunisia Gulf of Hammamet Gulf of Gabès Malta Southern Sicily Northern Adriatic Sea Southern Adriatic Sea Western Ionian Sea Eastern Ionian Sea Southern Ionian Sea Aegean Sea Crete Northern Levant Sea Cyprus Southern Levant Sea Eastern Levant Sea Marmara Sea Black Sea Azov Sea

Studied area X X X n.a. X X X n.a. X X X X n.a. n.a. n.a. n.a. X X X X X n.a. X n.a. X X X n.a. X X n.a.

Several factors compete for the ingestion/assimilation of MPs by marine organisms such as size, density, abundance, and colour. For what concern size, smaller MPs are the most bioavailable. For the density, the greater the quantity of MPs present, the greater the possibility of ingestion and/or adsorption, as well as for the abundance, a greater variety of MPs involves a greater percentage of organisms be attracted to these particles. Finally, for what concerns the MPs colour, studies demonstrated that certain colours tend to attract some groups of organisms, all these factors cause an increase in the

2.2  Microplastics and Posidonia oceanica Egagropyls

15

bioavailability of microplastics in organisms with respect to other anthropogenic waste (Alomar et al. 2017; Ory et al. 2017). Procter et al. (2019) showed that microplastics after weathering process release volatile organic compounds, such as dimethyl sulphide (DMS), a compound present in algae that generate an olfactory mark attracting the zooplankton, which mistakes the MPs for their prey. MPs have many ecological impacts on the marine fauna because, they can be ingested by many marine organisms and enter the marine food web (Wang et al. 2016). MPs are similar in size to zooplankton (0.3–5 mm), and can lead to confusion for predators regarding planktonic prey of this size they can be ingested by marine zooplankton (Desforges et al. 2015), and transfer from mesozooplankton to macrozooplankton (Setälä et al. 2014). In addition, the MPs transfer was found in marine invertebrates species such as Mytilus edulis and Carcinus maenas (Farrell and Nelson 2013), this discovery is very important because proves that MPs can reach higher trophic levels (Wright et al. 2013a, b). As reported by several authors (Andrady et al. 2011; Valente et al., 2019; Bottari et al. 2019, 2022a, b) MPs have also reached the highest trophic levels, such as elasmobranchs (Mancuso et al. 2022) or big pelagic fish (Xiphias gladius, Thunnus thynnus, Thunnus alalunga) (Romeo et al. 2015, 2016). The impact of MPs on marine organisms depends on a combination of specific parameters, such as the position of these microparticles in the water column (Van Cauwenberghe et al. 2015), the polymers and additives composing them, and the organism ingestion systems. Moreover, these microparticles can act as vectors for several toxic chemicals, that are adsorbed onto the surface, across the food web (Tanaka et al. 2013). Many marine species are concerned, some of which are edible, representing potential impacts on human health (Mancuso et  al. 2021; Huang et  al. 2021). Although several studies have shown that MPs are ingested by different species, their mechanisms and effects are still poorly understood. The aims of this chapter were: (i) to have an overview of MPs pollution in different Mediterranean GSAs; (ii) to understand if and which marine species are most affected; (iii) to highlight the most frequently polymer isolated, (iv) to show the techniques used to isolate and characterize MPs; (v) to verify if there are gaps in the studies carried out (Fig. 2.1).

2.2 Microplastics and Posidonia oceanica Egagropyls Posidonia oceanica is a Mediterranean endemic marine plant forming lush, extensive meadows from 0.5 to 40 m of water depth. P. oceanica has long, ribbon-like leaves, with a clear differentiation in leaf blade (photosynthetic) and leaf base (non-­ pigmented and fibrous) that attaches the leaf to the stem, called rhizome (Hartog and Kuo 2006). P. oceanica loses leaves in autumn, which are washed by waves and currents, and accumulate on adjacent beaches as wrack beds; during the burial

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Fig. 2.1  Mediterranean Geographical Sub-Areas (GSAs) – FAO- Res. GFCM/33/2009/2 on the establishment of geographical subareas in the GFCM area of application. (From www.fao.org/ gfcm/data/gsas/en/)

process, leaf sheaths, which are rich in lignocellulose, suffer mechanical erosion, releasing part of the constituent fibers that intertwine to form ball-shaped agglomerates known as sea balls, Neptune balls or aegagropilae (EG) (Pietrelli et al. 2017). These balls can trap several marine microplastics both in seawater and beached. Pietrelli et al. (2017) found for the first time in Latium beaches (GSA 9) the presence of microfibres entrapped in the EG, the most abundant polymers in EG were PA, PE, cotton, and PET mixing, the size 60 °C and produces large amounts of foam during the digestion process. For these reason scientists are trying to find a new method to isolate microplastics (Roch and Brinker 2017; Yu et al. 2019). Bai et al. (2022) reported that KOH was the most commonly used isolation method, followed by H2O2 and HNO3.

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Several studies were performed to find the best method to isolate MPs but to date, there is not one method that prevails over the others, in fact, all have both advantages and disadvantages, depending essentially from the polymeric nature. Cole et al. (2014) reported that the alkaline digestion method (KOH or NaOH), the most frequently used, if on the one hand is rapid and allow the digestion of organic matter, on the other hand can easily destroy nylon, PE and PES because of the high pH. They also showed that the enzymatic digestion could be a good method because does not destroy MPs, but it is very expensive. Avio et al. (2015a, b) highlighted that the acidic digestion (HNO3) can melt MPs at high temperature, resulting in low recovery (4 ± 3%). Munno et al. (2018) showed that the oxidized digestion (H2O2) dissolves several MPs at >60 °C and produces large amounts of foam during the digestion process. For these reason scientists are trying to find a new method to isolate microplastics (Roch and Brinker 2017; Yu et al. 2019). Furthermore, is important highlight that, given the characteristics of microplastics, a set of techniques for their detection in marine biota were used since their discovery, among which those are: visual identification (human eye or microscopy), density separation and C:H:N analysis (separate by density), Pyrolysis-GC/MS (compare with pyrograms), Raman spectroscopy (monochromatic laser and compare the polymer spectra) and Fourier Transform Infrared (FTIR) spectrometer (infrared radiation producing molecular vibrations) (Rezania et  al. 2018) (see Fig. 2.12). For what concerns identification methods basing on found papers to write this chapter, the most used is FT-IR (64%), followed by a visual characterization 25%, the latter, although widely used, does not allow to characterize the isolated polymer

Fig. 2.12  Digestion methods

2.10 Conclusions

57 Raman 3%

μRaman 3%

DSC 3%

µFT-IR 2%

Visual 25%

FT-IR

Visual

FT-IR 64%

Raman

μRaman

DSC

µFT-IR

Fig. 2.13  Identification methods

and therefore it is a superficial method that will be lost over time, other techniques such as Raman or DSC (3% for both) are still little used (Fig. 2.13).

2.10 Conclusions Based on the bibliographical research carried out to date in Algeria, Corsica, Creta, Eastern Levant Sea Malta, Tunisia and Azov Sea no works concerning microplastics in marine biota have never been carried out or published (Table 2.2). These countries should be watched, studies should be carried out in the coming years in order to fill these gaps. Mullus barbatus was the most studied species, 16 scientific papers, followed by Sardina pilchardus, 12 papers. The most polluted part is the port of Alexandria in Egypt (GSA 26), in fact, as reported by Shabaka et al. (2020), the highest values in absolute abundance of microplastics were recorded. The most abundant polymers are PE, PET and PP. The pollution of marine microplastics has become more and more serious and has become a global pollution incident, but there is a lack of effective treatment methods. he presence of such different methodologies and without the same guidelines for all means that there can often be substantial differences both in terms of the size of the microplastics and the polymers characterized, so it would be appropriate to find guidelines that can standardize the methodology in order to make the studies comparable to each other.

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Future investigations will be necessary to explore any effects of plastic on marine fauna, and which can affect the extraordinary biodiversity that distinguishes the Mediterranean Sea.

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Gomiero A, Strafella P, Øysæd K-B, Fabi G (2019) First occurrence and composition assessment of microplastics in native mussels collected from coastal and offshore areas of the northern and Central Adriatic Sea. Environ Sci Pollut Res Int 26:24407–24416 Green DS (2016) Effects of microplastics on European flat oysters, Ostrea edulis and their associated benthic communities. Environ Pollut 216:95–103 Gündoğdu S, Cem C, Ataş N (2020) Occurrence of microplastics in the gastrointestinal tracts of some edible fish species along the Turkish coast. Turkish J Zool 44:312–323. https://doi. org/10.3906/zoo-2003-49 Güven O, Gökdağ K, Jovanović B, Kıdeyş AE (2017) Microplastic litter composition of the Turkish territorial waters of the Mediterranean Sea, and its occurrence in the gastrointestinal tract of fish. Environ Pollut 223:286–294. https://doi.org/10.1016/j.envpol.2017.01.025 Hartog C, Kuo J (2006) Taxonomy and biogeography of seagrasses. In: Seagrasses: biology, ecology and conservation. Springer, Amsterdam, pp 1–24 Hennicke A, Macrina L, Malcolm-Mckay A, Miliou A (2021) Assessment of microplastic accumulation in wild Paracentrotus lividus, a commercially important sea urchin species, in the Eastern Aegean Sea, Greece. Reg Stud Mar Sci 45:101855 Huang W, Song B, Liang J, Niu O, Zeng G, Shen M, Deng J, Luo Y, Wen X, Zhang Y (2021) Microplastics and associated contaminants in the aquatic environment: a review on their ecotoxicological effects, trophic transfer, and potential impacts to human health. J Hazard Mat 5(405):124187. https://doi.org/10.1016/j.jhazmat.2020.124187 Kazour M, Terki S, Rabhi K et al (2019) Sources of microplastics pollution in the marine environment: importance of wastewater treatment plant and coastal landfill. Mar Pollut Bull 146:608–618. https://doi.org/10.1016/j.marpolbul.2019.06.066 Kousteni V, Karachle PK, Megalofonou P (2017) Diet of the small-spotted catshark Scyliorhinus canicula in the Aegean Sea (eastern Mediterranean). Mar Biol Res 13(2):161–173. https://doi. org/10.1080/17451000.2016.1239019 Lefebvre C, Saraux C, Heitz O et al (2019) Microplastics FTIR characterisation and distribution in the water column and digestive tracts of small pelagic fish in the Gulf of Lions. Mar Pollut Bull 142:510–519. https://doi.org/10.1016/j.marpolbul.2019.03.025 Li Y, Sun Y, Li J, Tang R, Miu Y, Ma X (2021) Research on the influence of microplastics on marine life -3rd international conference on air pollution and environmental engineering. IOP Conf Ser Earth Environ Sci 631:012006. https://doi.org/10.1088/1755-1315/631/1/012006 López-Martínez S, Perez-Rubín C, Gavara R et al (2022) Presence and implications of plastics in wild commercial fishes in the Alboran Sea (Mediterranean Sea). Sci Total Environ 850:158025. https://doi.org/10.1016/j.scitotenv.2022.158025 Lusher A-L, Welden N-A, Sobral P, Cole M (2017) Sampling, isolating and identifying microplastics ingested by fish and invertebrates. Anal Methods 9:1346 Mancia A, Chenet T, Bono G et al (2020) Adverse effects of plastic ingestion on the Mediterranean small-spottedcatshark (Scyliorhinus canicula). Mar Environ Res 155:104876 Mancuso M (2019) Microplastics in Mediterranean Sea. J Mar Biol Aquasc. 1:1 Opinion Article Mancuso M, Savoca S, Bottari T (2019) First record of microplastics ingestion by european hake (Merluccius merluccius) in Tyrrhenian Sicilian coast (Central Mediterranean Sea). J Fish Biol 3:517–519 Mancuso M, Blasco J, Spanò N (2021) Microplastics in the Mediterranean Sea. Front Mar Sci 8:775765. https://doi.org/10.3389/fmars.2021.775765 Mancuso M, Panarello G, Falco F, Di Paola D, Serena S, Capillo G, Romeo T, Presti G, Gullotta E, Spanò N, Bono G, Giuliano S, Bottari T (2022) Investigating the effects of microplastic ingestion in Scyliorhinus canicula from the South of Sicily. Sci Total Environ 850:157875 Munno K, Helm P-A, Jackson D-A, Rochman C, Sims A (2018) Impacts of temperature and selected chemical digestion methods on microplastic particles. Environ Toxicol Chem 37:91–98 Nadal MA, Alomar C, Deudero S (2016) High levels of microplastic ingestion by the semipelagic fish bogue Boops boops (L.) around the Balearic Islands. Environ Pollut 214:517–523. https:// doi.org/10.1016/j.envpol.2016.04.054

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Chapter 3

Microplastics in Mediterranean Seawater

Abstract  Microplastic pollution is one of the global emerging threats. All oceans are contaminated by microplastics, in particular, the Mediterranean Sea, due to its characteristic semi-closed morphology and the different anthropogenic pressures exerted by the surrounding countries, is highly polluted. This chapter provides a collection of information on the abundance, origin, distribution, and composition of microplastics (MPs) reported in the sea surface and water column of the Mediterranean Sea. Several families of plastic polymers were found in Mediterranean waters, the chemical-physical characteristics of these polymers play an important role in the distribution of these particles in water bodies and in the interaction with Mediterranean marine fauna. The studies conducted to date showed a heterogeneous distribution and composition between the Mediterranean sub-basins. The heterogeneity of the MPs distribution could be related to several factors, such as the different methodological approaches, the effect of hydrodynamic characteristics, and water parameters. For these reasons a standardized protocol for water sampling, extraction, and identification of microplastics is strongly recommended. Finally, the evolution of marine litter modeling studies is recommended in order to understand the sources of litter, transport, and accumulation in the Mediterranean Sea. Keywords  Microplastics pollution · Mediterranean Sea · Sea surface · Seawater column · Distribution process · Fate

3.1 Introduction The presence of plastic debris in all ecosystems as well as in the most remote and wild marine ecosystems, such as the Artic sea and deepest marine seafloors (Barnes 2005; Obbard et al. 2014) was widely reported. Mismanaged wastes (such as littered, undisposed, or not recycled materials), generated by coastal populations, are the main source of plastic entering marine environments worldwide (Jambeck et al.

© The Author(s), under exclusive license to Springer Nature Switzerland AG 2023 M. Mancuso et al., Microplastics in the Mediterranean Sea, SpringerBriefs in Environmental Science, https://doi.org/10.1007/978-3-031-30481-1_3

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2015). Plastics, once in the sea, persist through centuries, going to fragmentation under the effect of photo-degradation, by UV radiations, and the action of environmental mechanical forces (waves and currents). The degradation process allows to the formation of smaller and smaller plastic pieces over time, up to the formation of microplastics (MPs) and nanoplastics (less than 5 mm and 1000 nm respectively). Every year about 130,000 tons of microplastics enter the European seas (European Commission 2018), and a huge percentage of these plastic fragments make their way to the Mediterranean Sea (Alessi et  al. 2018). The accumulation of floating plastic debris in the Mediterranean Sea was first reported by (Morris 1980) which highlighted the presence of about 1,300 plastics per square kilometer in the central area of the basin. Unfortunately, the knowledge of the real abundance of these pollutants and their distribution in the Mediterranean Sea is still fragmentary. The highest plastic concentrations were detected near the most populated and urbanized centers, with the areas most impacted represented by the Cilician Sea, the Catalan Sea, the NW Adriatic Sea, and the Gulf of Lion. Moreover, it was also detected the presence of local hotspots of plastics, such as the Saronic Gulf in the Aegean Sea, the Buna-Bojana plume in the Adriatic, the Gulf of Naples in the Tyrrhenian Sea, the Malaga Bay and the Gulf of Arzew in the Alboran Sea, the Gulf of Tunis, and the Abu Qir Bay (Liubartseva et  al. 2018). Concerning the plastic input in the Mediterranean Sea, part of the floating plastics can come from the Atlantic, as suggested by the hydrodynamic patterns of the basin (Soto-Navarro et al. 2010). However, most of the plastic pollution is strictly related to a large number of rivers (e.g., Po, Nile, Rhone) which, passing through densely populated and urbanized areas, flow into the basin carrying many pollutants and debris (Lebreton et  al. 2012; Lechner et  al. 2014; Liubartseva et  al. 2018; Prevenios et  al. 2018). Furthermore, most of the samplings carried out are concentrated on the presence of these pollutants on surface waters, with less attention on the water column (Simon-­ Sánchez et al. 2022). The study of MPs transport is challenging because includes physical, chemical, and biological processes (Andrady 2011). Moreover, the physical properties (e.g., size, shape, density, buoyancy) of microplastics, which can vary considerably, influencing their transport (Ballent et  al. 2012, 2013; Kowalski et al. 2016). The aim of this chapter was to summarize the progress of studies on the source, occurrence and fate of MPs in the surface and water column of the Mediterranean Sea, including the microplastics distribution process occurring in water environment, and to identify knowledge gaps in these topics. Understanding the real implications of the distribution and abundance of microplastics in the various aquatic compartments is of fundamental importance as the aquatic matrix hosts a wide range of species at risk of microplastics ingestion.

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3.2 Horizontal Transport of Microplastics in the Marine Environment Several hydrodynamic processes, such as currents, tides, and waves are the main agents of horizontal dispersion of microplastics from their sources. The floating microplastics are passively transported by complex physical flows, resulting in wide variability in surface concentrations. Often the largest currents, at basin and regional scale, carry the MPs to remote regions, while the coastal currents tend to beach them (Cole et al. 2011; Auta et al. 2017), and then bring them back into the sea, or in the case of the Mediterranean Sea, large areas of accumulation are due to surface slicks (Cole et al. 2011; Cózar et al. 2014; Pinto et al. 2016; Van Sebille et al. 2020). Along these zones of convergence floating objects show a high concentration. Wind also affects the distribution of floating plastics. In fact, in addition to the current driven by the wind, the wind waves induce the Stokes drift, which may be locally responsible for the transport of microplastics in shallow coastal waters. Land transport of drift microplastics in coastal waters is caused by a combination of surface residual currents, wind, and Stokes drift (Kako et al. 2014; Liubartseva et al. 2016).

3.3 Vertical Transport and Settling of Microplastics in the Marine Environment Microplastics can float on the seawater  surface but can also be suspended in the water column. Several studies highlighted a discrepancy between the observed and predicted plastic concentrations in surface waters (Cózar et al. 2014; Eriksen et al. 2014), obtaining very different, and more or less homogeneous vertical dispersion results depending on the oceanographic characteristics of the study area. Some authors reported a greater abundance of MPs near the sea surface and shown  a decrease in their abundance along the water column (Dai et al. 2018; Song et al. 2018), confirming the results of a previous study on the MPs distribution along the vertical profile of the upper water column and the link with the wind-induced mixing (Kukulka et al. 2012). On the contrary, other authors suggest that water density stratification affects the vertical distribution of plastic debris (Song et al. 2018). The general hypothesis is that the vertical MPs distribution in the water column is determined by the joint effects of both advection transport and turbulent mixing forces, suggesting that regional differences may occur in the vertical transport and distribution of MPs. In addition, the intrinsic properties of microplastics, such as density, size, or shape itself, can influence the vertical distribution of the MPs (Ballent et al. 2012). Enders et al. (2015) showed that larger microplastics are much less affected by turbulent mixing. Moreover, the lighter particles of seawater (e.g. polyethylene) are expected to move within the higher layers of the water column (Reisser et al. 2015).

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Other studies have found a close correlation between the physical characteristics of water (temperature and salinity) with the density of plastic particles (Dai et al. 2018; Van Sebille et al. 2020). In addition, other factors, such as biofouling (the process of accumulation of organisms on submerged surfaces), also contribute to modifying the density of microplastics and consequently their expected distribution in the water column. In turn biofouling, can be influenced by various factors such as polymer type and surface, surface energy, and roughness of the MPs (Kaiser et al. 2017).

3.4 Concentration and Polymeric Composition of Floating Microplastics in the Mediterranean Sea One of the first studies on the evaluation of floating particles in the Mediterranean Sea concerned the central and western areas (Ruiz-Orejón et  al. 2016), results showed an average concentration of 147,500 items/km2, estimating that the abundance of floating MPs in the entire Mediterranean basin amounted to a total value of 1455 tons of dry weight (DW). One of the most investigated areas of the Mediterranean basin is the Adriatic Sea, a study showed an average concentration of 406,000 MPs per km2 highlighting that over 80% of MPs were polyethylene (PE) (Gajšt et al. 2016). According to Gajšt et al. (2016), a study on the sea surface of the Slovenian stretch of the Adriatic Sea reported the presence of 472,000 ± 201,000 items/km2 of MPs, mostly represented by polyethylene (PE - 80%)(Politikos et al. 2017). Another study in the north-western Adriatic Sea highlighted the influence of river discharges on plastic pollution in the marine environment showing that the highest MPs concentrations were detected next to the Po Delta (4,300,000 particles/ km2). Significant spatial and temporal variations in MPs concentration appear to be closely related to the surface currents in the Mediterranean area, confirming that the highest concentrations of plastic particles is in the northern part of the basin and the northern Adriatic coast of Italy (Liubartseva et al. 2018). Moreover, some authors highlighted differences in MPs distribution linked to the seasonal variations, showing the highest density of floating plastic during the winter (Kovač Viršek et  al. 2016) (Carlson et al. 2017)(Arcangeli et al. 2018). In the north-western Mediterranean Ryan et al. (2009) evaluated the abundance of microplastics in the neuston layer and showed an average particle concentration of 116,000 items/km2 over the entire investigated area. High accumulation zones in the near-shore region have also been observed in the north-western Mediterranean coasts (Pedrotti et  al. 2016). Heterogeneous spatial distribution of MPs was observed in the Gulf of Lion between 2014 and 2016, with an average MP concentration of 112,000 items/km2 (Schmidt et al. 2018). Spatial variability was visible even on a small scale a few kilometers away from one sampling station to another. This can be explained through an evaluation of the potential sources of MPs which in this case correspond to the Rhone River, the densely populated areas, such as Marseille, and the industrialized coasts bordering the northwestern Mediterranean Sea. Furthermore, the Northern Current contributes to the dispersion of MPs from the input areas to the wider regions.

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Indeed, coastal pressures are also affected by hydrodynamic conditions. For example, in the Balearic Sea the greatest concentration of particles was 4,576,115 items/ km2 North of the Balearic islands (Ruiz-Orejón et al. 2018). The high concentrations of plastic reported on the coast of Ibiza and Mallorca in sparsely populated locations therefore, suggest that the distribution of the plastic particles was mainly influenced by the hydrodynamic conditions. Caldwell et  al. (2019) evaluated the presence of floating MPs in the Ligurian Sea and the Tyrrhenian Sea showing that the average concentration was 28,917 items/km2. Furthermore, the presence of slicks on the sea surface seemed to play a key role in the distribution pattern of MPs and the highest concentrations were recorded at these formations. The distribution patterns of floating surface microplastics (MPs) were investigated in the Ionian, Aegean, and Levant seas in relation to their sources and sea surface circulation, showing that the most abundant polymers were polyethylene (PE), polypropylene (PP), polystyrene (PS), and polyamide (PA) (Adamopoulou et al. 2021). The shape of the MPs also varied between the investigated areas, fragments (50–60%), filaments (1–23%), and films (3–26%). Another study along the Lebanese coast (Eastern Mediterranean basin) Kazour et al. (2019) showed very high concentrations of MPs in water samples with abundances of 6.7 MPs/m3. In the Southern part of the Mediterranean Sea, some floating patches of MPs were found. These were evaluated at 17 sites along the Israeli Mediterranean coast (van der Hal et al. 2017) which showed an average abundance of 1,518,340 items/km2. In some cases, MPs were found floating in large patches. One of these slicks contained an exorbitant number of plastic particles 64,812,600 items/km2, with average abundance values 1-2 orders of magnitude higher than reported abundances elsewhere in the world. In samples from the surface waters of Turkey, the abundance of floating MPs ranged from 16,339 to 520,213 items/km2 (Güven et al. 2017). Gündoğdu and Çevik (2017) investigated the effects of multiple flood events on the abundance of MPs in Mersin Bay (Turkey), in the north-eastern Mediterranean region, over a period of time between December 2016 and January 2017. The number of microplastics showed a 14-fold increase, ranging from 539,189 items/km2 before the flood period to 7,699,716 items/km2post-flood, and a predominance of both pre and post-flood of PE (Table 1 shows the Floating microplastics concentration in the Mediterranean Sea). As can be easily noted, the description of microplastic contamination levels in the Mediterranean is not a simple matter. Furthermore, the comparison of the results of the different areas is not possible for countless reasons, including high spatial and temporal variability of the distribution of floating particles due to the influence of sources (whether maritime or terrestrial), river discharges, hydrodynamic and meteorological conditions and including extreme climatic events. Moreover, scientific studies very often present differences in methodological approaches, including samplings, net size, and analytical approaches used to identify particles. Overall, the Mediterranean Sea is characterized by strong space-time variability in surface MPs concentrations, mainly due to the oceanographic conditions of the different areas, and for which model-based assessments make one of the largest contributions.

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3.5 Concentration and Polymeric Composition of Microplastics in the Water Column of the Mediterranean Sea The presence of plastics with different sizes and polymeric compositions was widely reported at all depths and in all habitats (Cózar et al. 2015; Suaria et al. 2016; Erni-Cassola et al. 2019). Concerning polymeric diversity, it follows all the global production stock of plastic materials (Suaria et al. 2016). The polymers PE and PP are found in high concentration in the entire basin, especially in the upper layers of the water column (being their density lower than seawater), and their presence increases proportionally to the distance from land. The Adriatic Sea showed a heterogeneous polymeric composition, with a wide presence of plastics (467.79 ± 1133.88 g/km2). Polymer composition was related to ship-­ based pollution, with the presence of paint chips and paraffin wax in addition to polystyrene, polyvinyl chloride, and polyvinyl alcohol. The presence of paraffin wax (widely used for insulation and impregnation) has highlighted the impact of the tank-washing residues, legally discharged at sea (Turner 2010; Song et al. 2014). Indeed, large quantities of these chemicals are transported using cargo ships which, due to the tank- washing, can be inadvertently dumped into the sea, together with other pollutants (Suaria et al. 2018). The highest plastic particles concentration in terms of weight (10.43 kg/km2) was detected from the western and central Mediterranean sub-basins, especially in the Corsica Channel (between Cap Corse and Capraia island) (Suaria et al. 2016), with PE and PP as the most abundant polymers and the most homogeneous composition if compared to the Adriatic sub-basin (Suaria et al. 2016; Fossi et al. 2017). Concerning the Tyrrhenian Sea (Tuscany), Baini et al. (2018) and de Lucia et al. (2018)  showed that PE was the most abundant polymer, followed by PP, PS, ethylene-­vinyl acetate (AVA), and styrene butadiene (SBR), while the plastic abundance in the water column was 0.26 items/m3 and 0.3 items/m3 respectively. The MPs distribution toward the water column increased near the bottom and the surface, decreasing in between intermediate layers, according to plastic dimensions, shape, and polymeric composition, as reported worldwide (Reisser et  al. 2015). Smaller plastics particles and filaments seem to be more susceptible to vertical transports, with seasonal mixing mechanisms of sea strata strongly affecting their vertical distribution (Kukulka et al. 2012; Van Sebille et al. 2015; Kooi et al. 2016; De La Fuente et al. 2021). In the Gulf of Lion, it was reported an abundance of 1 MPs/m2, with a large concentration of PE and PP as in a great part of the Mediterranean Sea. It was also detected an important concentration of PA which, despite its high density, was distributed also in relative superficial strata (Pedrotti et al. 2016; Fossi et al. 2017). The best-known industrial application of this polymer is to produce nylon, widely used to make fishing lines. This area showed a high concentration of plastic in the entire water column, with a maximal concentration below the surface (Lefebvre et al. 2019).

3.5  Concentration and Polymeric Composition of Microplastics in the Water Column…

73

The polymer concentration showed a strong seasonality, especially regarding PE and PP, higher concentrations of PE are reported in summer than in winter related to the intensive touristic activity characterizing this zone of the Spanish coast. While, PP showed higher concentrations in winter than in summer, being this polymer mainly used in building materials. Building activities reach their maximum intensity far from summer, showing once again how the several polymeric distribution and diversity are strictly related to the human activities acting in the different areas. Going westward along the Iberian coast, up to the Alboran Sea (Rios-Fuster et al. 2022), it was observed a decreasing trend in plastic abundance going from north to south, with the highest plastics abundance (8.4 items/L) reported on the northern Levantine coast at 50 m of depth and 5- 10 km of distance to the coast. At this distance from the coast, plastic abundance was higher in deep strata (below 50 m of depth) than shallower ones (above 50 m of depth), while, within the 5 km, deep and shallower strata showed similar plastic abundances. The overall plastics concentrations were 1.61 ± 1.06 items/L and 2.14 ± 1.73 items/L in shallower and deep strata respectively. The high level of plastic pollution in the northern Levantine coast was strictly related to the presence of many rivers (such as Ebro, Xúquer, Segura) and cities. Indeed, rivers operate as direct sources of microplastics in marine environments (Simon-Sánchez et al. 2019; Guerranti et al. 2020). The impact of debris and wastewater transported by rivers was also confirmed by the microplastics’ polymeric composition reported in the area. Indeed, it was characterized by high levels of low-density polyethylene and polypropylene, followed by polystyrene, polyethylene terephthalate, polycarbonate and polyoxymethylene. Especially low-density polyethylene and polypropylene are also found in wastewater treatment facilities related to textile washing (Naji et al. 2021). Concerning their vertical distribution, it showed a decreasing abundance trend from sub- surface to deeper strata, with polyethylene terephthalate as the predominant polymer in the water column. The polymer stratification was in accordance with their chemical features, with polymers denser than seawater (as polyvinyl chloride) deeply distributed in the water column. Unlike other geographical areas (Dai et al. 2018; Van Sebille et al. 2020), vertical and horizontal polymeric distribution in the Iberian Peninsula was not influenced by the oceanographic features of the different strata. While, concerning the Alboran Sea, the high energy showed by the Atlantic water entering from Gibraltar allowed the lowest level of plastic pollution reported for the entire Mediterranean basin (< 1 item/L) (Soto-Navarro et  al. 2010, 2020). This transit area with sub-basin water exchanges (Mansui et al. 2015) is considered as a dispersion area, together with the Ligurian and Tyrrhenian Sea, since the plastics showed lower concentration in the marine environment than the average. Regarding the Eastern Mediterranean sub-basin, several debris distribution models and simulations showed as the currents acting on it operate as debris particles attractors, allowing the large amounts of plastic detected especially in the south easterareas of the sub-basin (Mansui et al. 2015; Politikos et al. 2017, 2020). This was in line with the high occurrence of plastics particles and fragments detected in the Israeli coastal waters (7.68 ± 2.38 items/m3) and in the Turkish territorial waters

74

3  Microplastics in Mediterranean Seawater

(ranging from 16339 to 520 213 items/km2), characterized by a large percentage of PE, PA, PP, polyethylene terephthalate (PET), polyurethane (PU), and polystyrene (PS) (Gündoğdu 2017; Güven et al. 2017; van der Hal et al. 2017; Kazour et al. 2019). As stated above for other geographical sub areas, in addition to the peculiar circulation of superficial water, the intense human activities (as fisheries) acting in the area, together with the presence of several estuaries of highly polluted rivers (such as Ceyhan), allowed to this massive plastic pollution. As reported for the entire Mediterranean basin, PE was the most abundant polymer in the sub-basin in the subsurface, while PP and PS dominated the deepest strata of the water column (Kazour et al. 2019). The central Mediterranean sub-basin was also characterized by high level of polyolefins (PE and PP) by a large amount of ethylene-propylene copolymer (EPDM) in the waters of the Gulf of Gabes, with a microplastics abundance ranging from 25.471 to 111.821 items/km2 (Zayen et al. 2020). This class of plastic polymer is typically used to produce manufacturing carried bags. The overall polymeric composition and vertical distribution of plastic debris in the Mediterranean Sea were in line with those reported worldwide in the marine environments (Erni-Cassola et al. 2019), with the most abundant polymers represented by PE, PP, and PS. Their distribution in the water column was related to the different polymer densities, but it was also influenced by several biotic (such as biofouling, inclusion in fecal pellets after ingestion, and incorporation in marine snow) and abiotic factors (such as water mass circulation, mixing phenomena driven by winds, and currents) as confirmed by the presence of low-density polymers also in the intermediate strata. The most polluted layers were the sub-superficial and the supra-benthic, with a high plastic abundance reported in the entire water column in several sub-area, as the Gulf of Lion and Iberian coastal waters. The high abundance of microplastics near the estuaries and urbanized centers confirmed the strict relation between human activities and plastic pollution; the polymeric composition can be an indicator of the source of contamination affecting the different areas. From a future perspective, further analysis of the vertical polymer distribution should be performed to understand at the destiny of the anthropogenic substances once entered the sea. This is essential to deepen the knowledge of the possible source of contamination for the organisms inhabiting the marine different habitats.

3.6 Effect of Sampling Methods on Microplastics Estimation 3.6.1 Surface Waters The absence of a standardized sampling protocol for the quantification of floating MPs complicates the comparison of pollution levels between the different areas of the Mediterranean.

3.6  Effect of Sampling Methods on Microplastics Estimation

75

Several studies evaluated the abundance, distribution, and composition of floating microplastics in the Mediterranean Sea. Most of these studies were based on sea surface sampling using Neuston and Manta trawl nets. The main advantage of this method is that large volumes of water are sampled in a relatively short time. The Marine Strategy Framework Directive (MSFD) for monitoring MPs recommend the use of a mesh size of 333 μm (Gago et al. 2016). Although several studies were carried out on the best mesh size, i.e., Dris et al. (2015) in a study conducted on the surface waters of the Seine, observed that the concentrations of MP analyzed with meshes with a size of 80 μm were 30 times greater than those collected with a 330 μm net. Kang et al. (2015) reported using a manual 50 μm mesh the fluctuating MPs concentration were two orders of magnitude higher than those obtained with a 330 μm mesh. It is therefore clear from the existing literature that the lower abundances of MPs coincide with the use of networks with larger mesh sizes. The smallest mesh size (52 μm) was used by Kazour et al. (2019) to collect samples from the Lebanese coast. The predominance of MPs samples from surface waters were collected using mesh sizes ≈333 μm (68.2%) and 200 μm (27.4%); this means that the smallest microplastics of this size ( 60

240–900c –

100c

141.20– 461.25

2175– 672

Fragments (%) –

> 60

> 60

–

87

Pellets (%) –

–

–

–

2

Granules (%) –

–

–

–

1

Foam (%) –

–

–

–

–

Films (%) –

–

–

–

–

Linesa (%) –

–

–

–

–

Membranes (%) –

–

–

–

–

Polymers –

–

–

PE, PP

PE, PP, PEP, PEst, PS, PAN, alkyd, PVC, PVOH, nylon

Identification method Stereo-­ microscope

Stereo-­ microscope

Stereo-­ microscope

FTIR-­ATR

μFT-IR

Alomar et al. (2016)

Alomar et al. (2016)

Alomar et al. (2016)

Abidli et al. (2018)

Vianello et al. (2013)

References

37.1.1

37.3.1

37.3.1

37.1.3

37.2.1

WMS

EMS

EMS

WMS

CMS

(Spain)

(Algeria)

Alicudi MPA (Italy) Tyrrhenian Sea

Gulf of Annaba

Samos Island (Greece)

Samos Island (Greece)

Tarragona

3

3 × 4 sites × each season

3 × 9 sites

3 × 9 sites

14

5

2–3

5–10

0–5

5

182.66– 649.33

6.1

14.7

Sieved with 347.9 4 mm, 2 mm, 1 mm and 63 μm steel sieves

Density and elutriation separation (Claessens et al. 2013; Thompson et al. 2004)

Density separation slightly modified (Thompson et al. 2004)

Density separation slightly modified (Thompson et al. 2004)

Sieve, visual 10.7 sorting and buoyancy in saturated NaCl and ZnCl2

85d

70

–

–

13

–

21

–

–

68

–

5

–

–

–

–

–

–

15 –

–

2

–

–

–

13

2

–

–

4

–

–

–

–

–

–

–

–

–

–

–

PE, PP, PET, PS, butyl branham, ethylene propylene, CTA

–

–

Stereo-­ microscope

FTIR-­ATR

Stereo-­ microscope

Stereo-­ microscope

PE, PP, PS, FTIR-­ATR, PET, Raman additive, U, spectroscopy silicone, PMA, PL, PA, synth. cellulose

(continued)

Fastelli et al. (2016)

Tata et al. (2020)

De Ruijter et al. (2019)b

De Ruijter et al. (2019)b

Expósito et al. (2021)

37.2.1

37.2.1

37.2.1

37.2.1

37.2.1

CMS

CMS

CMS

CMS

CMS

Sampling Area

Stromboli MPA Tyrrhenian Sea

Panarea MPA Tyrrhenian Sea

Lipari MPA Tyrrhenian Sea

Vulcano MPA Tyrrhenian Sea

Filicudi MPA Tyrrhenian Sea

Location

Table 4.1 (continued)

Country

(Italy)

(Italy)

(Italy)

(Italy)

(Italy)

N Samples

3

3

3

3

3

Sampling depth (cm) 5

5

5

5

5

N items/kg

Extraction process Sieved with 151.0 4 mm, 2 mm, 1 mm and 63 μm steel sieves

Sieved with 484.2 4 mm, 2 mm, 1 mm and 63 μm steel sieves

Sieved with 678.7 4 mm, 2 mm, 1 mm and 63 μm steel sieves

Sieved with 534.8 4 mm, 2 mm, 1 mm and 63 μm steel sieves

Sieved with 186.2 4 mm, 2 mm, 1 mm and 63 μm steel sieves

Fibers (%) 77d

62d

89d

63d

95d

–

–

4

–

–

–

–

2

Fragments (%) –

Pellets (%)

–

Granules (%) –

–

–

–

–

Foam (%) –

–

–

–

–

Films (%) 19

38

11

35

5

Linesa (%) –

–

–

–

–

Membranes (%) –

–

–

–

–

Polymers –

–

–

–

–

Identification method Stereo-­ microscope

Stereo-­ microscope

Stereo-­ microscope

Stereo-­ microscope

Stereo-­ microscope

Fastelli et al. (2016)

Fastelli et al. (2016)

Fastelli et al. (2016)

Fastelli et al. (2016)

Fastelli et al. (2016)

References

37.2.1

37.2.1

37.2.1

37.2.1

37.2.1

37.2.1

CMS

CMS

CMS

CMS

CMS

CMS

Salina MPA Tyrrhenian Sea

Capalbio Tuscany Tyrrhenian Sea

Albenga Tuscany Tyrrhenian Sea

Osa Tuscany Tyrrhenian Sea

Talamone Tuscany Tyrrhenian Sea

Salina MPA Tyrrhenian Sea

4

(Italy)

(Italy)

3

4

4

(Italy)

(Italy)

6

3

(Italy)

(Italy)

Sieved with 219.1 4 mm, 2 mm, 1 mm and 63 μm steel sieves

Superficial Density separation

49.0– 153.5

Superficial Sieved with 466 and 0–50 4 mm, 2 mm, 1 mm steel sieves and density separation

Superficial Sieved with 453 and 0–50 4 mm, 2 mm, 1 mm steel sieves and density separation

Superficial Sieved with 282 and 0–50 4 mm, 2 mm, 1 mm steel sieves and density separation

Superficial Sieved with 62 and 0–50 4 mm, 2 mm, 1 mm steel sieves and density separation

5

–

>88

>88

>88

>88

88d

–