Microplastics in Marine and Freshwater Environments
Chapter 1: General introduction
1.1 Plastics in the environment: an overview 1.2 Microplastics
1.2.1 Definition and sources
1.2.2 Occurrence in marine environments and focus on the Mediterranean Sea: 1.2.2.1 A potpourri of microplastics in the sea surface and water column of the Mediterranean Sea
1.2.2.2 A snapshot of microplastics in the coastal areas of the Mediterranean Sea
1.2.3 Occurrence in freshwater environments
1.2.4 Hazardous substances associated with microplastics 1.2.5 Ingestion and ecotoxicological effects of MPs on biota 1.2.6 European legislation on microplastics
1.3 Thesis structure: main objectives and research questions
Chapter 2: Occurrence and Characterization of Microplastics in
Marine Environments
2.1 Microplastic in the surface waters of the Ross Sea (Antarctica): Occurrence, distribution and characterization by FTIR
Chapter 3: Occurrence and Characterization of Microplastics in
Freshwater Environments
3.1 Plastic litter in aquatic environments of Maremma Regional Park (Tyrrhenian Sea, Italy): Contribution by the Ombrone river and levels in marine sediments
3.2 Occurrence and characterization of microplastics in Vesijärvi and Pikku Vesijärvi Lakes, Finland
Chapter 4: Self-contamination in MPs research
4.1 There’s a fly in my … or is that microplastic?
Chapter 5: Ingested microplastic as a two-way transporter for
PBDEs in Talitrus saltator
Chapter 6: Oxidative stress response of Tubifex tubifex exposed
to microplastics
Chapter 1
General introduction
1.1 Plastic accumulation in the environment
The term plastic refers to a wide range of polymeric materials produced mainly from petrochemicals by addiction of various chemical additives. According to the characteristics required, it is possible to obtain different products selecting the type of monomers that act as subunits. Generally, the backbone chain of a polymer is composed of covalent bonds between carbon and hydrogen atoms and this, coupled with its high molecular weight, makes polymers rather resistant to degradation.
The low cost of production, the high versatility, the durability and good electrical and insulation properties ensured the success of plastic and its mass production has exponentially increased since the 1940-1950s (Thompson et al., 2009). According to Plastic Europe, in 2016 the global production of plastic was around 335 million tons, while in Europe was about 60 million tons. Data on the distribution of global plastic materials production are reported in table 1 (Plastic Europe 2017).
Table 1 distribution of global plastic materials production in Europe (Plastic Europe 2017)
Region Production of plastic materials (%)
Asia 50 (China 29, Japan 4)
Europe 19
North America 18
Middle East-Africa 7
South America 4
Commonwealth of Independent States 2
Plastic has become a key material in many business areas; the packaging sector represents for the 39.9% of the European plastics converter demand, followed by
building and construction (19.7%), automotive (10%), electrical and electronic (6.2%), household, leisure and sports (4.2%), agriculture (3.3%) and others (16.7%) (Plastic Europe 2017).
Single-use packaging items account for more than 10% of the municipal solid waste (Jambeck et al., 2015).
Polypropylene (PP), polyethylene (PE), polyvinyl chloride (PVC), polyurethane (PUR) and polyethylene terephthalate (PET) are the polymer types most in demand in Europe (Plastic Europe 2017) and these data reflect the composition of plastic litter found in the environment (Arutchelvi et al., 2008; Suaria et al., 2016).
The same characteristics that make plastic an advantageous and convenient material to use and produce, might become disadvantages when it is not useful anymore and is improperly discharged in the environment. Fishing nets, bags, bottles and other plastic items accumulate in the aquatic environments and it may take centuries for them to degrade. According to Derraik (2002) between 60% and 80% of all marine debris is made of plastic coming from both land and sea-based. UNEP (2005) estimated that about 20 million metric tons of plastic waste end up in the oceans every year and they can travel long distances from the release point and accumulate on seafloor or remote areas (Lusher et al., 2015; Cincinelli et al, 2017). Polymers are scarcely used as pure substances, they are usually combined with toxic additives to enhance their performance and to lower the production cost (Ivar do Sul and Costa 2013).
The survey currently available affirms that the oceans contain over 150 million tonnes of plastics and 23 million tons of additives (World Economic Forum, 2016). It has been estimated that about 225000 tons of these additives are released into the oceans annually and this number could rise to 1,2 million tons per year by 2050 (World Economic Forum, 2016).
The first report raising the awareness on plastic pollution on the surface of the North Atlantic date back to the early ‘70s (Carpenter and Smith, 1972). Carpenter and Smith stated in their Science publication: “the increasing production of plastic, combined with present waste-disposal practices, will probably lead to greater concentrations on the sea surface... At presence the only known biological effect of these particles is that they act as a surface for the growth of hydroids, diatoms, and probably bacteria”. Their prediction turned out to be forward-looking since a recent study found out that the plastic accumulation area in the Pacific Ocean called the Great Pacific Garbage Patch is four to sixteen times higher than predicted, estimating an average of 79 thousand tons of plastic
debris floating on a surface of 1.6 million km2 (Lebreton et al., 2018). In addition
to the floating plastic litter, there are other plastics that are not easily detectable because they sink into the sea bottom or distribute in water columns; even though many polymers have a lower density than water, microorganisms and invertebrates can colonize plastic surface creating microbial biofilms, which change the density of the materials and entail the inevitable sinking of the polymers (Avio et al., 2016).
Since the first report of Carpenter and Smith, the number of scientific publications on plastic pollution has grown exponentially. Plastic litter seems to be ubiquitous having reached the most remote areas on this planet, such as Antarctica (Cincinelli et al., 2017), Arctic (Lusher et al., 2015) and deep-sea sediments (Woodall et al., 2014). Plastic materials are so widespread and abundant in the environment that they could become a new key geological indicator of the Anthropocene (Zalasiewicz et al., 2016). Terrestrial plastic sources include river outflows, wastewater effluents and discharges along beach and coastal resorts due to tourism or recreational activities; whereas marine litter sources include extensive commercial fishing as well as recreational and
maritime activities. In particular, nets ropes and other plastic tools are invariably lost or discarded carelessly in the sea (Andrady, 2011).
In the last few years, plastic pollution has gained media attention and it has become an emerging environmental concern (Suaria et al., 2016), especially regarding the aquatic environment where the presence of these materials could represent a threat to the ecosystems and fauna (Cole et al., 2011).
1.2 Microplastics
1.2.1 Definition and sourcesWhereas large plastic items are easily detectable, there is a big portion of plastic pollution that is so small that is not visible to the naked eye, referred to as microplastics (MPs) and nanoplastics (NPs). NPs are defined as plastic fragments smaller than 0.2 mm (Wagner et al., 2014) but the definition of MPs is not clear yet.
The US EPA (2011) defines them as plastic particles smaller than 5 mm, while according to Browne et al. (2015) MPs are plastic items smaller than 1 mm with no specified lower limit of quantification reported. Duis and Coors (2016) have suggested to set the lower limit to 100 nm.
In comparison to macro and mesoplastic (> 25mm and 5-25 mm respectively) (MSFD 2013) MPs and NPs could represent a major threat for aquatic ecosystems and biota because of their smaller size (Besseling et al., 2014). MPs can be classified according to their origin as follows:
Primary microplastics are manufactured as pellets, microbeads or capsules. They include microbeads added in personal care products, such as toothpastes, facial cleaners, eye shadows, shower gel, nail polish, hair coloring and other cosmetics. Their content in the products may vary from
pre-production resin granules with a cylinder or disk shape, usually transported to industrial sites where plastics are made by melting and molding the pellets into the final products (Ivar do Sul and Costa, 2013). Resin pellets can be released into the environment during transport, manufacturing and accidental spills (Mato et al., 2011). Microplastics are also used in industrial scrubbers, printers, spray paints, and synthetic textiles.
Secondary microplastics derive from the degradation of larger pieces of plastic breaking down into smaller fragments (Cole et al., 2011) due to chemical, physical and biological processes that occur in marine and freshwater environments such as photo-degradation, biodegradation, photo-oxidative, thermo-oxidative degradation and hydrolysis. Degradation by solar UV radiation is particularly efficient because, once initiated, the cleavage of the bonds can continue thermo-oxidatively or some time without the need for further exposure to UV radiation (Andrady et al., 2011). Furthermore, degradation occurs faster in virgin pellets that contain no UV stabilizers (Andrady et al., 2011).
The alteration and loss of structural integrity of the polymer matrix takes place due to the presence of crosslinks, namely the formation of new bonds between the chains. This at last results in cracks or yellowing. Furthermore, plastic debris in the marine environment can rapidly accumulate microbial biofilms, which further permit the colonization of algae and invertebrates on the plastics surface increasing the density of the particles. Plastics become less buoyant over time and polymers
originally less dense than sea and freshwater, may sink(Cole et al., 2011)
With a loss of structural integrity, these plastics are increasingly susceptible to fragmentation resulting from abrasion, wave action, turbulence and stress induced by humidity and temperature changes (Cole et al., 2011). Fragments become smaller over time until they turn into micro- and nanoparticles of plastics. An important source of secondary MPs are synthetic clothes; it has been estimated that on average 1900 microplastic fibers can be discarded by a synthetic item (blankets, fleeces or shirt) during only one washing (http://ec.europa.eu/). Since the wastewater systems are not able to block MPs, the fibers will directly end up in the aquatic compartments.
1.2.2 Occurrence in Marine Environment and focus on the Mediterranean Sea Several literature studies have detected MPs in oceans, seas, shorelines, beaches, sands, sediments, surface waters and at all depths (Ivar do Sul et al., 2009; Thompson et al., 2009; Cole et al., 2011; Isobe et al., 2016; Barrows et al., 2018; Gago et al., 2018). The occurrence of MPs in marine environment seems to be ubiquitous since they have reached even remote areas such as the Arctic and Antarctic (Obbard et al., 2014; Lusher et al., 2015; Bergmann et al., 2017; Cincinelli et al., 2017; Waller et al, 2017).
In tables 2, 3 and 4 the abundance of microplastics in different marine compartments have been reported. As we can notice, MPs occurrence is not homogeneously distributed (Horton et al., 2017; Klein et al., 2018). This high discrepancy could be due to collecting site variability, sampling methods, human activities (Eerkes-Medrano et al., 2015), sample treatments and analysis (Mai et al., 2018). Another issue adding possible discrepancy between the studies is that there are no standardized and validated protocols for sampling, quantification, and characterization of MPs. This aspect is deeper examined in Chapter 4, while
the occurrence of MPs in marine environments, with a focus on the Mediterranean Sea, is further investigated in the following two subheadings.
Table 2 MPs density in marine waters (particles/m3)
Environmental
compartment (particles/mDensity 3) Location Reference
Open and coastal waters
0.01 to 2.6 New England coast Carpenter et al., 1972i
8 to 9180 NE Pacific Ocean Desforges et al., 2014 0.0014 California coast Doyle et al., 2011
0.02 Atlantic Ocean
Law et al., 2010
0.001 Caribbean Sea
0.001 Gulf of Maine
150 to 2400 North Sea Lozano and Mouat, 2009 2.46 NE Atlantic Ocean Lusher et al., 2014 Range 0 to 1.3 Artico surface water Lusher et al., 2015
0 to 11.5 Artico sub surface water
7.25 Coastal ocean near Long Beach, California Moore et al., 2002 3.05 California coast Moore et al., 2005 38 to 234 (ice) Arctic Ocean Obbard et al., 2014 6 to 14 *particles/L Belgian coast Van Cauwenberghe et al., 2013
0.167 Yangtze Sea, China Zhao et al., 2014 688.9 to 3308 Sud Africa Coast Nel and Froneman, 2015
0.17 Ross Sea, Antarctica Cincinelli et al., 2017
Bays
64000
Jade Bay, Germany Dubaish and Liebezeit, 2013 88000
3.92 Santa Monica Bay, California Lattin et al., 2004 12.000 Los Angeles River, USA Lattin et al., 2004
Table 3 MPs density in marine waters (particles/m2)
Environmental
compartment (particles/mDensity 2) Location Reference
Open and coastal water
0.116 NW Mediterranean Sea Collignon et al., 2012 < 1mm to 9.490 South Pacific Subtropical Gyre Eriksen et al., 2013b 31982 to 969777 North Pacific Central Gyre Moore et al., 2001
Bays < 1 to 563 Chesapeake Bay, USA Yonkos et al., 2014
Table 4 MPs density in marine sediments
Environmental
compartment Density Location Reference
Sand Fragments 1–15 mm 37.8 kg−1 Pellets 1–15 mm 4.9 kg−1 Hawaian Islands McDermid and McMullen, 2004
29 m−2 Russia Kusui and Noda, 2003
PS spheres 874 (±377) m−2
Fragments 25 (±10) m−2
Pellets 41 (±19) m−2
Heugnam Beach, South
Korea Heo et al., 2013 Pellets >1,000 m−2 Tokyo, Japan Kuriyama et al., 2002
Fragments and pellets 1–10 mm
30 m−2
Coastal beaches,
Chile Hidalgo-Riz and Thiel, 2013 Fragments and pellets
1–10 mm
805 m−2 Easter Island, Chile
Hidalgo-Riz and Thiel, 2013
160.08 particles/m2 Trinidad and Tobago
Tartaruga beach Ivar do Sul et al., 2017b Strait of Hormuz,
Persian Gulf
Naji et al., 2017a 1258 ± 291 particles/kg) (S2) > (S4) > (S1) Bostanu (S5 122 ± 23 particles/kg Gorsozan 26 ± 6 particles/kg Khor-e-Yekshabeh 14 ± 4 particles/kg Suru 2 ± 1 particles/kg Khor-e-Azini
Pellets 3–6 mm 1.289 m−2 Portuguese coast Antunes et al., 2013
Pellets and fragments 185.1 m−2 Portuguese coast Martins and Sobral,
2011
Pellets 0–2.500 m−3 Santos Bay, Brazil Turra et al., 2014
Fragments 40 items m−2 Southern Atlantic Van Cauwenberghe
et al., 2013b Fragments 20 and 50 kg−1 Harbor sediment, Sweden
Norén, 2007 Pellets a 3320 kg−1 Industrial harbor
sediment, Sweden Pellets a 340 kg−1 Industrial coastal sediment, Sweden
Fibres and granules 3,800 kg−1
d.w Spiekeroog, Germany Liebezeit and Dubaish, 2012 Fragments 1.3, 1.7, 2.3 kg−1
d.w. Norderney, Germany Dekiff et al., 2014
Fragments and fibres 672–2,175
kg−1 d.w. Venice lagoon, Italy Vianello et al., 2013
Pellets 10, 43, 218, 575 m−2 Kea Island, Greece Kaberi et al., 2013
31-105.4 pieces kg−1 Bohai Sea Dai et al., 2018
1.2.3.1 A potpourri of microplastics in the sea surface and water column of the Mediterranean Sea
Doctoral candidate contribution: Manuscript preparation
1.2.2.2 A snapshot of microplastics in the coastal areas of the Mediterranean Sea
1.2.3 Occurrence in Freshwater Environment
Literature studies conducted on MPs pollution in freshwater systems are still scarce if compared to the ones on MPs in marine environments.
Within MP research, less than 4% concerns freshwater environment (Eerkes-Medrano et al., 2018; Lambert and Wagner, 2018; Li et al., 2018) and thus there is a current need to collect data to establish the presence, the distribution and the impact of MPs in these aqueous systems.
Recent literature surveys have established that MP occurrence does not significantly differentiate between marine and freshwater bodies (Peng et al., 2017; Blettler et al., 2018). Similarly, to marine environments, MPs in freshwater systems seem to be ubiquitous and not homogeneously distributed (Horton et al., 2017; Klein et al., 2018; Lambert and Wagner, 2018) as it is showed in tables 5 and 6.
The occurrence and source of MPs in freshwater matrices, with a focus on both lacustrine and fluvial environments, is further investigated in the Chapter 3.
Table 5 MPs abundance in freshwaters
Environmental
compartment Density Location Reference
Estuaries 4137.3 particles/m 3
Yangtze Sea, China - estuary Zhao et al., 2014 500 to 10,000 particles/m3
Freshwater
808.2 particles/m3
Danube River, Austria Lechner et al., 2014 17.1 particles/m3
9 to 91 particles/m3
WWTP effluent to North Sea,
Netherlands Leslie et al., 2013 Mean – 52 particles/m3
1.94 to 17.93 particles/m3 North Shore Channel, Chicago,
USA McCormick et al., 2014 15,000 particles/m3 incoming water WWTP,
Sweden Magnusson K.,
2014 Mean 8 particles/m3 effluent water WWTP, Sweden
0.002 particles/m3 San Gabriel River outlet, USA Moore et al., 2002
30 to 109 particles/m3 California rivers, USA
Moore et al., 2005b 12,000 particles/m3 Los Angeles River, USA
average 892.777 particles
km2 Rhine river, Germany Mani et al., 2015
43,000
particles/m2 Great Lakes, Canada/USA
Eriksen et al., 2013a 1277 to 12,645 particles/m2 Lake Superior, Canada/USA
0 to 6,541 particles/m2 Lake Huron, Canada/USA
4,686 to 466,305
particles/m2 Lake Erie, Canada/USA
997 to 44,435
(particles/m2) Lake Hovsgol, Mongolia Free et al., 2014
192–13,617 particles km2 Three Gorges Dam, China Zhang et al., 2015
5.7-398.0 fibers m3 Marne river, France Dris et al., 2017
Mean: 91,000
items/km2 Swiss lakes, Switzerland Faure et al., 2012
Table 6 MPs abundance in freshwater sediments
Environmental
compartment Density Location Reference
Sediments
228 to 3,763 particles kg-1 Rhine, Germany Klein et al., 2015
786 to 1,368 particles kg-1 Main, Germany Klein et al., 2015
Maximum: 563 106 items/km2 Siling Co basin, China Zhang et al., 2016
Mean: 1,300 106 items/km2 Swiss lakes, Switzerland Faure et al., 2012
Range: 108–1108 Lake Garda, Italy Imhof et al., 2013 Range: 13.7–745.4 item/500
mL
Five urban estuaries of KwaZulu-Natal,
South Africa Naidoo et al., 2015
1.2.5 Hazardous substances associated with MPs
Generally, during the production process the basic polymer of a plastic material is combined with additives to improve its performances (Ivar do Sul and Costa 2013). The most common additives are colorants, stabilizers, plasticizers, antioxidants, UV absorbers, flame retardants, antistatic agents and other substances added in order to enhance the processing, increase the stiffness and mechanical characteristics of the product (Nerlan et al., 2014).
Since the polymerization process of monomers is often not complete and additives are not included in the polymeric structure the latter can be released during the plastic life cycle, from production to disposal (especially if exposed to UV radiation and heat) and they may pose environmental and health hazard (Oehlmann et al., 2009; Teuten et al., 2009; Halden et al., 2010; Lithner et al., 2011; Papaleo et al., 2011 Yang et al., 2011; Rochman et al., 2015).
From a chemical point of view these substances can be alkylphenols, phthalates, chlorinated compounds, aromatic compounds, metals, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), polybrominated
diphenyl ethers (PBDEs) and others (Hahladakis et al., 2018). Moreover, it has been demonstrated that MPs tend to sorb POPs (Persistent Organic Pollutants) from the surrounding environment (Moore 2008; Teuten et al., 2007; Lee et al., 2014), that are mostly insecticides, pesticides and industrial chemicals entering the ocean via waste- and run-off waters (Andrady, 2011).
The interaction between these organic substances and plastics depends on their physical and chemical properties (Nerland et al., 2014). Usually, the absorption of chemicals occurs on the amorphous regions of the polymers rather than the crystalline ones and thus different percentages of crystallinity determine different rate of diffusion and different capacity to absorb chemicals (Nerland et al., 2014). In aquatic environments, usually the highest concentration of POPs is found in the surface water, at the interface between water and air, where also plastics accumulate (Cole et al., 2011). Due to POPs hydrophobicity and low polarity, these organic substances tend to sorb into plastic surface and their concentration on MPs exceeds the one in surface water (Andrady, 2011).
There are several experimental evidences that prove the ability of polymeric material to sorb organic pollutants (Teuten et al., 2007; Bakir et al., 2014). Teuten et al. (2007) investigated the sorption of phenanthrene from seawater onto PE, PP and PVC. The contamination was conducted through a horizontal, rotary
agitation of a solution of 14C-labeled phenanthrene, plastic particles (200 - 250
µm) and seawater and the analysis showed that in all three cases, the uptake of the contaminants to plastics was highly greater than to natural sediments.
Bakir et al. (2014) demonstrated that virgin PVC and PE microplastic particles
(200-250 µm) are able to sorb 14C-DDT, 14C-phenanthrene (Phe),
14C-perfluorooctanoic acid (PFOA) and 14C-di-2-ethylhexyl phthalate (DEHP)
reaching the sorption equilibrium between plastic and seawater within 48 h. Another study investigated the capacity of low- and high-density polyethylene (LDPE/HDPE) to sorb six PAH compounds characterized for different polarities,
in order to detect possible differences in the sorption process. The results showed that LDPE sorbs PAHs faster than HDPE and that, independently from the polymer, the PAHs molecular weight is one of the parameters which influences the sorption process: the smaller the molecular weight, the higher the diffusion coefficient (Fries and Zarfl., 2011).
A Japanese research reported the presence of PCBs, nonylphenols (NPs) and dichlorodiphenyldichloroethylene (DDE) in polypropylene resin pellets collected in water and sediments from four coasts in Japan (Mato et al., 2001). Concentrations of DDE (0.16-3.1 ng/g), PCBs (4-117 ng/g) and NPs (0.13-16 µg/g) on pellets reflected the concentration on bottom sediment and suspended particles sampled from the same areas (Mato et al., 2001).
In 2005 a volunteer-based program called International Pellet Watch was launched with the aim to monitor the pollution status of the oceans. Dr. Hideshige Takada’s Laboratory of Organic Geochemistry at the Tokyo University of Agriculture and Technology received beached plastic resin pellets collected all over the world, which were analyzed to detect and quantify the presence of POPs in marine environments.
POPs associated with MPs are considered hazardous pollutants since they tend to accumulate in the environment, are toxic, possible carcinogen and able to influence the immune, reproductive and endocrine systems of animals (Frias et al., 2010).
Thanks to their ability to be transported by wind, rain and marine currents or to be absorbed by sediments, ground and suspended dust particles in the atmosphere, POPs have a global level distribution. Their density, boiling point, solubility in water, solubility in organic solvent, vapor pressure, partition coefficient and others chemical and physical properties, determine their fate in the various environmental compartments.
From 2001, measures have been taken to reduce or eliminate the use and production of POPs by the ‘Stockholm Convention’. This Convention is a negotiation stipulated by the United Nations (UNEP – United Nations Environment Programme) (http://unep.org/) including European Union (EU) member states (http://chm.pops.int). Initially 12 POPs, which belong to the categories of pesticides, industrial chemicals and by-products, were recognized as causes of negative effects on humans and ecosystems. Subsequently, other substances similar to POPs (in persistence, long range transport, bioaccumation and toxicity) were added to the Stockholm Convention (Zarfl et al., 2010). Although EU has called for actions to reduce and eliminate the production and use of intentionally produced POPs, these contaminants are still present in the environment; and they continue to be absorbed on microplastic particles and to bioaccumulate through the food chain.
Table 7 summarizes some studies conducted to assess the occurrence of organic contaminants on microplastics collected from aquatic environments. The high variability of pollutants concentration is probably due to the different type of polymer, type of contaminant, sampling site and time of residence of the plastic in the environment.
All these evidences underline that plastic debris are new environmental matrices able to accumulate POPs and that their role of sink for organic contaminants should be analyzed in order to understand the occurrence and the fate of chemical pollution into aquatic environments (Rochman et al., 2015).
Target pollutants
Sampling sites Plastic types Instrumental methods Pollutants concentrations References
PCBs California coastline
PE and PP resin pellets
Soxhlet extraction with dichloromethane and analysis by GC-ECD PCBs:23–605 ng/g www.pelletwatch.or g PAHs, PCBs, DDTs, chlordanes San Diego coastline (California) Pre-production pellets, plastic fragments, PS foam, and rubber
Sonication extraction and analysis by GC-MS PAHs: 30-1900 ng/g PCBs: from non-detect to 47 ng/g DDTs: from non-detect to 76 ng/g Chlordanes: 1.8-60 ng/g Van et al. 2011 PAHs, PCBs
San Diego Bay (California)
PET, HDPE, LDPE, PVC, PP pellets
Sonication extraction and analysis by GC-MS PAHs: 797 ng/g on HDPE, 722 ng/g on LDPE, 122 ng/g on PP, 14 ng/g on PET, and 27 ng/g on PVC. (Harbor Excursion) PCBs: 25 ng/g on HDPE, 34 ng/g on LDPE, 27 ng/g on PP, 1 ng/g on PET and 2 ng/g on PVC (Shelter Island) Rochman et al. 2013c PAHs, PCBs, DDT
Portuguese coast Resin pellets ASE 200 extraction and analysis by GC-MS and GC-ECD PAHs: 53-44800 ng/g PCBs: 2-223 ng/g DDT: 0.42-41 ng/g Antunes et al. 2013 PAHs, Santos Bay
(Brasil)
Plastic pellets Soxhlet extraction with dichloromethane and analysis by GC-MS
PAHs: 386-1996 ng/g Fisner et al. 2013 PCBs,
DDE, NP
Kasai Seaside Park, Keihin Canal, Kugenuma Beach and Shioda Beach (Japan)
PP resin pellets
Soxhlet extraction with hexane and analysis by capillary gas chromatograph equipped with ECD and MS detector PCBs: 4−117 ng/g DDE: (0.16−3.1 ng/g) NP: (0.13−16 μg/g) Mato et al. 2001 PCBs, DDTs, HCHs Remote islands (Pacific, Atlantic and Indian Oceans and Caribbean Sea)
PE pellets Soaking in hexane extraction and analysis by GC-ECD PCBs: 0.1-9.9 ng/g DDTs: 0.8-4.1 ng/g HCHs: 0.6-1.7 ng/g. In St. Helena Island 19.3 ng/g Heskett et al., 2012 PAHs, PCBs, DDTs PBDEs NP, OP BPA Remote beaches (RB) (Costa Rica and Vietnam) Open ocean (OC) (Central Pacific Gyre, Pacific Ocean, Caribbean Sea) Urban beach (UB) (Tokyo, Kanagawa, Los Angeles) PP and PE debris
Soxhlet extraction with dichloromethane and analysis by GC-MS PAHs: RB 1-2024 ng/g OC 12-868 ng/g UB 17-9297 ng/g PCBs: RB 1-102 ng/g OC 1-78 ng/g UB 2-436 ng/g DDTs: RB 0.6-124.4 ng/g OC 0-4.8 ng/g UB 0.2-198 ng/g PBDEs: RB 0.3-412 ng/g OC 0-3.9909 ng/g UB 0.02-230 ng/g NP: RB 0-3936 ng/g OC 5.8-997 ng/g UB 0-1244 ng/g OP: RB 0-154 ng/g OC 0.1-40.4 ng/g UB 0.2-198 ng/g BPA: RB 0-729.7 ng/g OC 0-283.4 ng/g UB 0-26.2 ng/g Hirai et al., 2011 Table 1 occurrence of organic contaminants on microplastics collected from aquatic environments
1.2.6 Ingestion and ecotoxicological effects of MPs on biota
The physical accumulation of MPs in the aquatic systems is an environmental issue that goes beyond the aesthetic problem and the damage caused to the touristic industry. In response to growing concerns from the scientific community regarding MPs contamination, the studies conducted on this topic are rapidly increasing. Despite the large number of papers published on this topic, there are still several gaps that need to be deeply investigated to understand MPs potential toxicological effects on biota.
What we know is that marine and freshwater biota can ingest microplastics by mistake exchanging it for food; seabirds, fishes, turtles, whales and crustaceans, such as amphipods, can mistake plastics for prey or ingest them alongside food items (Teuten et al., 2007; Cole et al., 2011; Ugolini et al. 2013; Auta et al., 2017). These synthetic materials, once inside the body, are not metabolized and thus can be accumulated or expelled by biota. Long-term effects consist on the damage of the intestinal apparatus, obstruction of the stomach and immediate satiety (Jimenez et al., 2015). The normal food cycle of biota could slow down leading to the death of the animal.
Literature studies have demonstrated that MPs could induce oxidative stress to the organisms able to ingest it (Jeong et al., 2016; Lu et al., 2016) but the effects of MPs on marine and freshwater biota are still quite unknown and there is a current need to gather data to understand the impact of MPs.
To date, Browne et al. (2013) studied the effect of MPs on the oxidative status of lugworms (Arenicola marina) demonstrating that animals exposed to PVC micro particles were more susceptible (> 30%) to oxidative damage. A Chinese study showed that after 7 days of exposure to PS microplastics, the freshwater fish
Danio rerio (zebrafish) exhibited a higher oxidative stress than the controls, revealed by the increase of the activity of Superoxide Dismutase (SOD) and catalase (CA) (Lu et al., 2016). Deng et al. (2017) tested the effect of fluorescence PS microplastics in mice, revealing alterations of CAT, SOD and GPx levels and indicating the potential health risk MPs represent to biota.
Since MPs tend to sorb POPs, ingested MPs could represent a feasible vector to transfer the associated chemicals into the fatty tissue of animals (Browne et al., 2013).
Residual monomers from manufacture, additives and pollutants sorbed from the environment may leach out of the ingested plastic, become bio-available to the organisms, contaminate the biota and enter the food chain (Andrady et al., 2011). Furthermore, POPs and microplastics can biomagnify into organisms at higher trophic levels and amplify their concentration through the food web (Teuten et al., 2009).
One of the first cases of ingestion of plastic resin pellets contaminated with PCBs was reported in 1970 (Rayan et al., 1988). This study evidenced a positive correlation between the mass of ingested plastics and PCB concentrations in the fatty tissue of Great Shearwater, Puffinus gravis.
More recent studies (Besseling et al. 2013; Browne et al., 2013; Chua et al., 2014; Scopetani et al., 2018) have evidenced that ingested MPs may transfer substances able to damage the endocrine systems and influence mobility functions, development, and reproduction of various organisms.
Rochman et al. (2014b) found a positive link between plastic debris density and chemical burden of BDE#s 183 –209 in fish tissues. Furthermore, same authors (Rochman et al., 2014) showed that the occurrence of higher brominated congeners, added to plastic as flame retardants, could be used as markers of plastic pollution in the aquatic environments.
More recently, Batel et al. (2016) studied the transfer of organic contaminants to biota through the food chain, evidencing that ingested microplastics spiked with benzo[a]pyrene (BaP) by Artemia sp. Nauplii transferred the hazard to the animal and furtherly to zebrafish (Danio rerio) via predation of contaminated Artemia. In the last few years, the scientific community has considered the hypothesis that microplastic could also act like a scavenger of POPs. A first experiment performed by Teuten et al. (2007), showed that clean microplastics added to sediments contaminated with POPs seemed to lower the concentrations of the pollutants in this matrix (Teuten et al., 2007). Authors hypothesized that clean microplastics may lower POP concentrations in many environmental compartments such as water, sediments and food (Koelmans A. A., 2015) reducing the bioavailability of contaminants for biota. Indeed, ingested microplastics could be able to absorb the chemicals already present in the gut of the animals and reduce the biomagnification (Gouin et al., 2011).
In order to migrate from plastic to biota and vice versa, a gradient driving the organic contaminants is needed (Gouin et al., 2011; Koelmans et al., 2013, 2013b).
However, Teuten et al. (2007) supposed that the cleaning mechanism of plastic in biota may be strongly limited considering that plastic items can last a very long time in the aquatic environments adsorbing high pollutants concentrations from the surrounding sea surface water.
The scavenger role of MPs is not deeply delved in the scientific literature and there is an urgent need to collect experimental data to support the role played by MPs as a two-way carrier/vector of contaminants Koelmans et al. (2016).
1.2.7 European legislation on microplastics
Plastic and microplastic pollution have recently gained media attention and in the last few years the increasing concern about the effects on the environment and the impact on food for human consumption has set political action in motion. The marine litter issue has been addressed for the first time in the Marine Strategy Framework Directive (MSFD; full title: Directive 2008/56/EC of the European Parliament and of the Council of 17 June 2008 establishing a framework for community action in the field of marine environmental policy). Through eleven descriptors, this directive requires to EU Member States with marine territories to set up measures to reach and maintain the Good Environmental Status (GES). Descriptor 10 deals with marine litter that is defined as “any persistent, manufactured or processed solid material discarded, disposed of or abandoned in the marine and coastal environment. Marine litter consists of items that have been made or used by people and deliberately discarded or unintentionally lost into the sea or coastline including such materials transported into the marine environment from land by rivers, drainage or sewage systems or wind. For example, marine litter consists of plastics, wood, metals, glass, rubber, clothing, paper etc. This definition does not include semi-solid remains of for example mineral and vegetable oils, paraffin and chemicals (Galgani et al., 2010).
Descriptor 10 “requires EU Member States to ensure that, by 2020, properties and quantities of marine litter do not cause harm to the coastal and marine
environment.”
(http://ec.europa.eu/environment/marine/good-environmental-status/descriptor-10/index_en.htm)
Furthermore, on 16th January 2018 the European Commission adopted a Strategy for Plastics that includes marine plastic and microplastic pollution as one of the three major areas discussed. Some of the initiatives undertaken by the Strategy are as follows:
“Consideration of measures against Single Use Plastics and fishing gear: the Commission adopted its proposal in May 2018 - "Be ready to change!"
Assessment of the need to restrict microplastics intentionally used in products under REACH and request to European Chemicals Agency (ECHA) to prepare a restriction dossier, on the basis of a Commission study regarding microplastics intentionally added in products.
Consideration of measures against microplastics generated during the life cycle of products, on the basis of another Commission study.
The Commission also presented its proposal for amending the Port Reception Facilities Directive, aiming inter alia to reduce marine litter from ships,
including fishing vessels and recreational craft.”
(http://ec.europa.eu/environment/marine/good-environmental-status/descriptor-10/index_en.htm)
1.3 Thesis structure: main objectives and research questions
In response to growing concerns from the scientific community regarding MPs contamination, the studies conducted on this topic are rapidly increasing, but despite the rapid growth, there are still several questions in MP monitoring and aquatic toxicological aspects that need to be investigated and better understood. Some of the key research questions stated in the present research study are the following:- What is the extent of MPs pollution in marine and freshwater environments?
- Are the current sampling techniques, sample handling, and morphological, physical and chemical characterization analysis of MPs able to provide reliable data?
- What are the risks to marine and freshwater organisms associated with MPs?
- What are the impacts of MPs ingestion on marine and freshwater biota? - Does MP act as a carrier or a scavenger of organic contaminants for
aquatic biota?
The interdisciplinary nature of the project, combining expertise in analytical chemistry, ecology and ecotoxicology, promotes a sound and innovative research. The main aim of the thesis is to evaluate the potential risks posed by MPs to marine and freshwater environments, while the specific aims of the project and the related Chapters are reported below:
Aim 1 __________Chapter 1, Chapter 2 and Chapter 3
The two review studies reported in Chapter 1 provide an overview on the risks associated to the occurrence of MPs in the Mediterranean Sea; A picture of MP levels in the Mediterranean coastal environments is given, evidencing information gaps and considering also estuary, lagoons and areas influenced by the contribution of rivers.
Comparing the number of MP studies conducted in the marine environment with the ones regarding freshwater systems, a remarkable discrepancy can be observed. Within MP studies, less than 4% concerns freshwater environment (Lambert and Wagner, 2018) and thus there is a current need to collect data to establish the occurrence and the impact of MPs in these aqueous systems. To provide new information about the distribution, abundance and characterization of MPs in freshwater and marine ecosystems (water, sediments,
ice and snow samples) Ross Sea (Antarctica), Ombrone and Albegna rivers (Italy), Vesijärvi and Pikku Vesiärvi Lakes (Finland) are investigated. Data comparison allows to evaluate differences in microplastic pollution between remote and urban aquatic environments. Furthermore, the determination of the type of microplastics in the samples is fundamental for the choice of the microspheres used to contaminate marine and freshwater biota.
Aim 2 __________Chapter 4
To investigate the probability and amount of self-contamination resulting from sampling attire while performing MPs studies.
Aim 3 __________Chapter 5
To deep the knowledge about the fate of the pollutants associated with MPs investigating the MP role as potential vector and/or scavenger of contaminants in Talitrus Saltator (T. saltator).
Aim 4 __________Chapter 6
To evaluate the toxicological effects of microplastics in Tubifex tubifex, a freshwater tubificid worm often used in toxicity test. Tubifex worms are exposed to florescent PE microspheres to evaluate the possible oxidative stress induced by MPs.
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Chapter 2
Occurrence and Characterization of Microplastics in Marine
Environments
Doctoral candidate contribution: Conventionalization and experimental design, Sampling, Analysis, Manuscript preparation
