Open access peer-reviewed chapter

Microplastics in Aquatic Environments and Their Toxicological Implications for Fish

Written By

Cristóbal Espinosa, M. Ángeles Esteban and Alberto Cuesta

Submitted: 09 March 2016 Reviewed: 05 July 2016 Published: 26 October 2016

DOI: 10.5772/64815

From the Edited Volume

Toxicology - New Aspects to This Scientific Conundrum

Edited by Sonia Soloneski and Marcelo L. Larramendy

Chapter metrics overview

3,612 Chapter Downloads

View Full Metrics

Abstract

The intensive use of plastics and derivatives during the last century has increased the contamination of animal habitats. The breakdown of these primary plastics in the environment results in microplastics (MP), small fragments of plastic typically <1–5 mm in size. Apart from the potential negative effects of the MPs per se, it is generally assumed that microplastics may increase the exposure of marine aquatic organisms to chemicals associated with the plastics. In addition, to enhance the performance of plastics, additives are added during manufacture. Furthermore, they are active in absorbing other contaminants and be used as vectors of highly and well‐documented persistent contaminants. Finally, these small MPs are easily ingested by animals and affect their physiology and behaviour. Thus, aquatic living organisms are continuously exposed to these MPs, and associated contaminants, and could suffer from its contamination but also introduce them into the food chain.

Keywords

  • Microplastics
  • toxicants
  • aquatic environment
  • fish

1. Introduction

The production of synthetic polymers has increased more than 100‐fold since the middle of the twentieth century to reach the 280 million tonnes of plastics produced annually worldwide
most of which is destined for disposable use [1]. High production coupled with the physical characteristics of most plastics, such as their chemical inertness and very slow biodegradation rates, results in an accumulation of plastic debris in the environment [2]. Routes of discharge such as improper waste disposal, insufficient waste management and urban run‐offs [3] may lead to significant amounts of these plastics entering the aquatic environment [4, 5]. It is a long‐recognized fact that marine plastic debris contaminates the oceans and seas of all the world [3, 6, 7]. In the marine environment, plastics undergo a process of weathering and fragmentation that breaks down macrodebris into smaller micro‐ and nanodebris. This fragmentation of plastic is caused by a combination of mechanical forces, for example waves and/or photochemical processes triggered by sunlight. Some ‘degradable’ plastics are even designed to fragment quickly into small particles, although the resulting material does not necessarily biodegrade [8].

The terms ‘microplastics’ (MP) and ‘microlitter’ have been defined differently by various researchers. Gregory and Andrady [9] defined microlitter as the barely visible particles that pass through a 500‐µm sieve but are retained by a 67‐µm sieve (≈0.06–0.5 mm in diameter), while particles larger than this were called mesolitter. Others [1012] defined the MPs as being in the size range <5 mm (recognizing 333 µm as a practical lower limit when neuston nets are used for sampling). Microplastic particles may further fragment into ‘nanoplastics’, a term that has not been defined uniformly in the literature, and may refer to <100‐µm particles of plastic [13].

Microplastics have been accumulating in the environment for nearly half a century and are found in oceans worldwide [3] including in the Antarctic [7]. Despite this worldwide dissemination of plastic fragments, the global load of plastics on the open ocean surface has been estimated to be far less than might be expected, but nevertheless increasing. Thus, the potential effects of microplastics on marine ecosystems are still far from being well understood [14]. It is believed that the virging MPs are not chemical contaminants to marine organism, but they can produce physical problems such as digestive congestion. However, they can be loaded with many substances to fit the virgin MPs to industry and consumer demand (e.g. additives, preservatives, etc.). In addition, these MPs can also adsorb contaminants present in the environment and act as vectors. Therefore, in this chapter, we shall summarize some important aspects of the microplastics found in the marine environments and some of the effects described in fish biota.

Advertisement

2. Chemical nature

Plastics are usually synthesized from fossil fuels, but biomass can also be used as feedstock. The most commonly used plastic materials, the also called virgin plastics, are polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polystyrene (PS) and polyethylene terephthalate (PET), which, together, represent approximately 90% of total world plastic production [15]. They are elements of high molecular weight and are non‐biodegradable and therefore extremely persistent in the environment. PE, PP, PVC, PS, PET and polyurethane (PUR) are widely used resins (29, 19, 12, 8, 6, and 7% of global production, respectively) [16]. Plastics present many advantages since they are inexpensive, water‐ and corrosion‐resistant, chemically inert, easily moulded and exhibit good thermal and electrical insulating properties. However, plastics also present many disadvantages, being non‐renewable resources and sources of contamination by additive compounds; they suffer embrittlement at low temperatures and deformation under loads; they need costly recycling processes and are highly resistant to degradation, etc. The behaviour of plastics in the environment will differ according to their chemical nature and physical properties. A reflection of this is the description of microplastics found in marine environments in different studies (Table 1).

Polymer type  % Studies (n) 
Polyethylene (PE)  31 (33) 
Polypropylene (PP)  25 (27) 
Polystyrene (PS)  16 (17) 
Polyamide (nylon) (PA)  6.0 (7) 
Polyester (PES)  3.7 (4) 
Acrylic (AC)  3.7 (4) 
Polyoxymethylene (POM)  3.7 (4) 
Polyvinyl alcohol (PVA)  2.8 (3) 
Polyvinyl chloride (PVC)  1.8 (2) 
Poly methylacrylate (PMA)  1.8 (2) 
Polyethylene terephthalate (PET)  0.9 (1) 
Alkyd (AKD)  0.9 (1) 
Polyurethane (PU)  0.9 (1) 

Table 1.

Frequency of occurrence of different polymer types in microplastic debris sampled at sea or in marine sediments [17].

Advertisement

3. Sources

Microplastics comprise a very heterogeneous assemblage of particles that vary in size, shape, colour, chemical composition, density, and other characteristics. They can be subdivided according to their usage and source into (i) ‘primary’ MPs, produced either for indirect use as precursors (nurdles or virgin resin pellets), for the production of polymer consumer products or for direct use, for example in cosmetics, scrubs and abrasives and (ii) ‘secondary’ MPs, which result from the breakdown of larger plastic material into smaller fragments [18].

3.1. Primary: common consumer products

Microplastics (e.g. PE spheres) are used in personal care products such as toothpaste, facial and exfoliating creams, even though many consumers are not aware of this. In some cases, these MPs have replaced natural materials, such as seeds, shells or ground pumice ingredients. Usually, they are not filtered during wastewater treatment and are usually released directly into the sea or other water bodies such as lakes and rivers. Microplastics are also found in synthetic textiles: wastewaters from washing synthetic clothes, such as shirts, contain more than 100 fibres per litre of water. According to a study by Browne et al. [19], on average, about 1900 MP fibres can be released in a single machine wash. Similar fibres have been observed in wastewater effluent and sludge near large urban centres.

3.2. Primary: industrial sources of microplastics

Plastic pellets are the raw material of plastic products. They are typically spherical or cylindrical in shape and millimetres in diameter. In addition, pellets are used in various industrial applications, including as ingredients of printing inks, paints spray, injection mouldings and abrasives [20]. A proportion of MPs used in these industrial applications enters the environment. The improvement in the management of operations in which plastic pellets are used could be a clear way to prevent them from entering the environment.

3.3. Secondary: plastic waste as a source of microplastics

Secondary microplastics are formed when larger plastic items are broken down. The rate at which fragmentation occurs is highly dependent on environmental conditions, especially temperature and the amount of UV light available [20]. Plastic debris can enter the ocean directly or can reach it through other water bodies or the atmosphere. The key to stopping plastic ‘ocean trash’ is to prevent such waste from entering the environment in the first place. Obviously, larger objects are easier to identify and control than smaller objects. About half of the world’s population lives within 100 km of the coast, with an increasing population in that area. It is therefore highly likely that the amount of plastic waste entering the ocean from land‐based sources will increase if significant changes are not made in the waste management on land.

Advertisement

4. Ecosystem distribution

The accuracy of MP emission estimates is currently hindered by lack of data. More specifically, information on MP transport efficiency in run‐off and streams is missing. This is despite the large number of qualitative studies on microplastics in rivers and sediments [2124]. Similarly, only limited assessments of MPs from sewage and canalizations, their retention by wastewater treatment plants and release by effluents are available [25, 26].

One of the most important factors affecting microplastic distribution in marine waters is the density of the materials (Table 2). Materials whose specific density is less than that of marine water (∼1.02) may be located on the surface, while materials with a specific density greater than that of marine water may be sink (Table 2). Thus, being buoyant in water, PE and PP float in seawater and mainly affect ocean surfaces and deposits ashore [27, 28], while PVC, which is denser than seawater, affects the seabed, often next to the source [27].

Categories  Common applications  Specific density*
Polyethylene (PE)  Plastic bags, six‐pack rings  0.91–0.94 
Polypropylene (PP)  Rope, bottle caps, netting  0.90–0.92 
Foamed polystyrene (PS)  Cups, buoy  0.01–1.05 
Polystyrene (PS)  Tools, packaging  1.04–1.09 
Polyvinyl chloride (PVC)  Bags, tubes  1.16–1.30 
Polyamide or nylon  Rope  1.13–1.15 
Polyethylene terephthalate (PET)  Bottles  1.34–1.39 
Polyester resin+fibreglass  Textiles  >1.35 
Polycarbonate (PC)  Electronic compounds  1.20–1.22 
Cellulose acetate  Filter cigarettes  1.22–1.24 
Polytetrafluoroethylene  Teflon, tubes  2.1–2.3 

Table 2.

Common applications and specific density of some plastics found in the marine environment.

*Specific density expressed in g/cm3. The density of plastics may change depending on additives and environmental processes. Based on References [5, 29, 30].


Location  Microplastic concentrations  References 
Pacific Ocean  27,000–448,000 particles per km2 [33, 34] 
370,000 particles per km2 [35] 
0.004–9200 particles per m3 [36, 37] 
Atlantic Ocean  2.5 particles per m3 [38] 
Indian Ocean  81.43 mg per kg* [39] 
Mediterranean Sea  0.16 particles per m2 [40] 
0.62 particles per m3 [41] 

Table 3.

Microplastic concentrations observed in oceans of the world.

*Sediment samples.


Moreover, the colonization of MPs by microalgae and other microorganisms increases plastic density, which has been shown to affect the vertical transport of MPs in an aquatic environment and their long‐term distribution [31]. However, the chemical composition, particularly as a result of low amounts of additives, may partially explain the changes in microbiological colonization from one type of polymer to another. Also, for the same type of polymer, the chemical composition can vary considerably depending on chemical additives and the time passed in the environment. Hence, the distribution of MPs in the ecosystems may change according to these parameters, too. Long et al. [32] recently showed that MPs could be incorporated in microalgal homo‐aggregates, demonstrating the existence of a pathway of vertical transport of MP from the surface layer to the floor of the ocean.

In addition, MP concentrations and/or quantities differ between sampling sites (Table 3). A significant variation between the microplastics sampled in different oceans is evident, but there are also differences between the areas of the same ocean or sea. Published works have detected different concentrations of MPs depending on the proximity to populated and/or contaminated areas.

Advertisement

5. Absorption of toxicants

To enhance the performance of plastics, additives are added during manufacture, such as reinforcing fibres, fillers, coupling agents, plasticizers, colorants, stabilizers (halogen stabilizers, antioxidants, ultraviolet absorbers and biological preservatives), adsorbed chemicals, and unreacted starting materials (monomers), processing aids (lubricants and flow control), flame retardants, peroxide, antistatic agent, and plasticizers [16, 42], which may leach out under conditions of use and accumulate in the environment [43]. Apart from the potential negative effects of the MPs per se, it is generally assumed that microplastics may increase the exposure of marine aquatic organisms to chemicals associated with the plastics, such as persistent organic pollutants (POPs) or plastic additives [4447]. Thus, analytical study of marine MPs has revealed the composition of many toxicants adsorbed to them.

Additive  CAS  Log KOW Water solubility (mg/L) 
UV stabilizers
Benzophenone  119‐61‐9  3.18  None 
Benzotriazol  95‐14‐7  1.44  1.98 × 104
Antioxidants
Irganox 1024  32687‐78‐8  7.79  <1 
Irganox 1098  23128‐74‐7  –  0.1 
Irganox 1076  2082‐79‐3  <6  <0.01 
Irganox 1010  6683‐19‐8  ≈23  <0.01 
Irganox 168  31570‐04‐4  >6  <0.005 
Plasticisers
Dimethyl phthalate  131‐11‐3  1.61  4.2 × 104
Diethyl phthalate  84‐66‐2  2.38  1.1 × 104
Di‐n‐butyl phthalate  84‐74‐2  4.45  112 
Butylbenzyl phthalate  85‐68‐7  4.59  2.7 
Bis(2‐ethylhexyl) phthalate  17‐81‐7  7.5  0.003 
Di‐n‐octyl phthalate  3‐1307  8.06  0.02 
Lubricants
n‐Hexadecanoic acid  57‐10‐3  7.17  0.04 
Oleic acid  112‐80‐1  7.64  None 
Glycerol tricaprylate  538‐23‐8  9.20  0.40 (37°C) 
Isopropyl myristate  110‐27‐0  7.17  2.44 × 10-2
1‐Eicosanol  629‐96‐9  8.70  1.5 × 10-3
2‐Hexyl‐1‐decanol  2425‐77‐6  6.66  0.1727 
Octadecanamide  124‐26‐5  7.292  None 
4‐Methyl‐benzenesulfonamide  70‐55‐3  0.82  3.16 × 103
Hexacosanol  506‐52‐5  11.65  1.438 × 106
Decanedioic acid, bis(2‐ethylhexyl)  122‐62‐3  9.63  None 
Fuel
Pentadactyl ester trichloroacetic acid  74339‐53‐0  –  – 
1,10‐[2‐methyl‐2‐(phenylthio)cyclopropenylidene] bisbenzene  56728‐02‐0  –  – 
2,4‐dimethyl‐4‐octanol  568123  3.51  188.9 
Hexadecyl ester trichloroacetic acid  74339‐54‐1  9.1  6.223 × 10-5
Intermediates
HEHA  59130‐69‐7  11.15 4.127 × 106
2,3‐Dihydroxypropyl ester hexadecanoic acid  542‐44‐9  4.364  None 
Hexadecanoic acid ethyl ester  628‐97‐7  7.74 3.71 × 103
Behenic alcohol  661‐19‐8  9.68 1.5 × 105
Nonanoic acid  112‐05‐0  3.42  284 
Pimaric acid  127‐27‐5  6.60 9.232 × 102
3,5‐Di‐tert‐butyl‐4‐hydroxy phenyl propionic acid  20170‐32‐5  4.48  12.93 
Abietic acid  514‐10‐3  6.51 8.96 × 102
Dehydroabietic acid  1740‐19‐8  6.35 8.161 × 102
Monomers and oligomers
Bisphenol A  80‐05‐7  3.32  300 
4‐Hydroxyacetophenone  99‐93‐4  1.42  2.32 × 104
4‐Hydroxyacetophenone  99‐96‐7  1.58  5 × 103
Flame retards
PCBs  1336‐36‐3  3.76–8.26  2.7–1.5 × 104
PBBs  67774‐32‐7  6.5–9.4  – 
PBDE  5.52‐11.22  5.6 × 10-10–0.13 
‐tetraBDE  40088‐47‐9  5.87–6.16  1.1 × 10-2
‐pentaBDE  32534‐81‐9  6.57  13.3 × 10-3
‐hexaBDE  36483‐60‐0  6.86–7.92  4.2 × 10-6
‐heptaBDE  68928‐80‐3  9.44  2.2 × 10-7
‐octaBDE  32536‐52‐0  6.29  5 × 10-4
‐nonaBDE  63936‐56‐1  11.22  5.6 × 10-10
‐decaBDE  1163‐19‐5  6.265  – 
α‐HBCD  134237‐50‐6  5.07  48.8 
β‐HBCD  134237‐51‐7  5.12  14.7 
γ‐HBCD  134237‐52‐8  5.47  2.1 
TBBP‐A  79‐94‐7  4.5  720 
BTBPE  37853‐59‐1  7.88  19 
DBDPE  84852‐53‐9  11.1  21 
Anti‐DP syn‐DP  13560‐89‐9  9.3  250 
Others
7,9‐Di‐tert‐butyl‐1‐oxaspiro(4,5)deca‐6,9‐diene‐2,8‐dione  82304‐66‐3  3.59  15.5 
Glycerol 1‐palmitate  32899‐41‐5  6.17  0.1252 
(Z)‐13‐docosenamide  112‐84‐5  5.3  0.2 
Di‐tert‐dodecyl disulfide  27458‐90‐8  6.1  None 
1‐Hexadecanol  36653‐82‐4  6.83  4.1 × 10-2
Oleic acid eicosyl ester  22393‐88‐0  13.609  – 
Octadecanoic acid  57‐11‐4  8.23  0.568–0.597 
Octadecanoic acid 4‐hydroxy‐methyl ester  2420‐38‐4  –  – 
Tridecanoic acid 4,8,12‐trimethyl‐methyl ester  5129‐58‐8  –  – 
Succinic acid  110‐15‐6  -0.59  8.32 × 104
Triclosan  3380‐34‐5  4.76  12 

Table 4.

Log KOW and water solubility of main additives of microplastics. Based on References [5362].

In recent model analyses, however, it was shown that the effects of plastic on the bioaccumulation of POPs may be small, due to a lack of gradient between POPs in plastic and biota lipids, and that a cleaning mechanism is likely to dominate at higher log KOW (octanol/water partition coefficient) values [44, 48, 49] (Table 4). In the case of additives, monomers or oligomers, which are components of the plastics, this issue has hardly been addressed. Many substances such as plasticizers may have biological effects even at low concentrations in the ng/L or μg/L range [50]. Although it has been argued that exposure to additives will probably be low because of the low diffusivities of the chemicals, bioaccumulation could increase the concentration in animal tissues. Moreover, POPs, like the bisphenols or nonylphenols found in plastics, have been suggested to be a relevant environmental problem [51]. It has been reported that the concentrations of bisphenol A in wild freshwater fishes oscillated from undetected to 25.2 μg/kg biomass, while nonylphenol levels varied from 1.01 to 277 μg/kg [52]. So, the substances can enter and be accumulated by animals, and the log KOW could give an idea of the behaviour of additives in aquatic environments and their solubility in water (Table 4).

5.1. Hydrocarbons

Hydrocarbons are organic compounds comprising only carbon and hydrogen atoms. The molecular structure comprises a frame of carbon and hydrogen atoms and grouped into saturated (straight, substituted and cyclic alkanes), unsaturated (alkenes with straight, branched and cyclic), halogenated and aromatic hydrocarbons. The hydrocarbons can be classified into two types—aliphatic and aromatic. Aliphatic hydrocarbons in turn can be classified into alkanes, alkenes and alkynes as link types that bind the carbon atoms. The general formulas of alkanes, alkenes and alkynes are CnH2n+2, CnH2n and CnH2n-2, respectively. Many alkanes with a chain length varying from C‐11 to C‐31 have been found in plastics from coastal debris [16]. These are other oligomers originating from polyolefins (polypropylene, polyethylene and poly(acetylene: styrene)) during recycling [63]. Octadecane (n = 20/43), hexadecane (n = 19), eicosane (n = 18), tetradecane (n = 18), heptacosane (n = 14), heptadecane (n = 13), pentadecane (n = 11), tetracosane (n = 10), docosane (n = 8), dodecane (n = 7), hexacosane (n = 7), 2,6,10‐trimethyl‐tetradecane (n = 10) and heptadecane, 3‐methyl‐ (n = 6) were the most frequently detected in the plastic debris from near the coasts [16].

Linear alkanes, together with iso‐alkanes, originate from the paraffin wax that is used as an external lubricant in PVC and other polymers, where they help the polymers to slide over other surfaces. Alkanes are also used as a solvents, such as hexane and heptane. Alkenes (squalene and others) and cycloalkenes are used as starting compounds for several additives and polymers and are formed as by‐products during olefin polymerization.

Aromatic hydrocarbons, such as benzene and anthracene derivatives, have also been found in MP debris. Benzene is an important organic chemical compound used mainly as an intermediate to make other chemicals, mainly ethylbenzene, cumene, cyclohexane, nitrobenzene, and alkylbenzene. More than half of the entire benzene production is processed into ethylbenzene, a precursor of styrene, which is used to make polymers and plastics like polystyrene and expanded polystyrene. Around 20% of benzene production is used to manufacture cumene, which is needed to produce phenol and acetone for resins and adhesives. The plastics may also carry halogenated hydrocarbons, which have been considered as POPs and are of proven toxicity [64, 65].

5.2. UV stabilizers/absorbers

Benzophenone and its derivatives are used as photo‐initiators in the UV curing of inks and as UV absorbers. These compounds absorb the harmful UV light that would eventually change the physical and optical properties of the polymer and make the material lose colour or fade. This substance can also be added to plastic packaging as a UV blocker to prevent photo‐degradation of the packaging polymers or contents. Its use allows manufacturers to package the product in clear glass or plastic [66] since, without the UV blocker, opaque or dark packaging would be required. These plastic additives are used in PP, PE (2–3%) and acrylonitrile, butadiene and styrene (ABS) copolymer products. Benzotriazole UV stabilizers (BUVS) are emerging contaminants that are mutagenic, toxic, pseudopersistent, bioaccumulated and show significant estrogenic activity [6770]. Great amounts of BUVS have been detected in rivers from Japan and China coming from wastewater treatment plants [7173]. Due to their common use, BUVS have been found in aquatics environments [69, 72, 74], organisms [71, 72, 74, 75], tap water and well water [76]. Recent findings in German rivers and previously reports suggest that BUVSs have a potential of long‐range transport, similar to several POPs [74].

5.3. Antioxidants

Antioxidants are widely used in plastic polymers to delay oxidation and to improve polymer properties [77]. Several types of antioxidants can be used to prevent the aging of plastic, such as phenolic antioxidants, organophosphorus compounds and different amines. However, antioxidants can migrate from the plastics into the food and contaminate it during production or storage, potentially giving rise to food safety issues [78, 79]. Antioxidants are used in almost all commercial polymers in small amounts up to 2% (w/w) (20,000 mg/kg or ppm) [16]. The polymers can be oxidized during synthesis, processing, transfer or final use, resulting in loss of chemical, optical and mechanical properties, among others. Thermal oxidation results in the formation of free radicals that react with oxygen to form hydroperoxides. In order to inhibit the onset of thermal oxidation of polymers and/or slow down degradative processes, the antioxidant additives are added during manufacture, processing and/or during the manufacture of the products. In the specific case of the polypropylene, antioxidant additives are important because the chemical structure of this type of polyolefin tends to degrade easily. The plastic antioxidants identified in the literature are usually limited to the commonly used Irganox series (including Irganox 1010, Irganox 1076, Irganox 168) [8084].

5.4. Plasticizers

Plastic as a material may contain a variety of chemicals, some potentially hazardous. Plasticizers, which are used to make the plastic soft and flexible, are mainly used in PVC, but they are detected in other polymer plastics. Several types of plasticizers are found in plastic debris, but phthalates predominate [85]. The phthalates found in plastics include dimethyl phthalate (DMP), diethyl phthalate (DEP), di‐n‐butyl phthalate (DBP), butyl benzyl phthalate (BBP), bis(2‐ethylhexyl) phthalate (DEHP) and di‐n‐octyl phthalate (DNOP) [86]. Their concentrations in different plastics vary widely; for example, in foodstuffs, the content of phthalates varies from 658 to 1610 ng/g fresh weight [87]. Phthalates are produced in large quantities around the world and are also widely used in cosmetics, plastics, carpets, building materials, toys, medical and cleaning products.

Several cross‐sectional and case‐control studies have reported an association between exposure to phthalates and the development of certain human allergies and respiratory diseases [88]. A recent systematic review based on less than ten relatively small (N < 400) studies found that the findings from these studies are inconsistent, with both decreases in birthweight and null associations, and both longer and shorter gestational periods being recorded [89]. A prospective birth cohort study researched the association between butyl benzyl phthalate and an early‐onset eczema, although not the late‐onset eczema, finding that prenatal exposure to butylbenzyl phthalate may influence the risk of developing eczema in early childhood [90]. Three studies reported a positive relation between prenatal exposition and the risk of wheeze, asthma and respiratory infections in children aged 5–11 years [9193], although, even here, there were inconsistencies concerning the phthalate congeners implicated [94].

On the other hand, phthalates have been related with hormone disorders [95], abortion [96], metabolic diseases [97], hormone disturbances, reprotoxicity or even suspected cancer [98100]. Other plasticizers are often used as substitutes for phthalates, but their effects on the health are not always clear, usually because of the limited data available. Therefore, because the amount of plasticizers could increase the 50% of the total weight, and the possibility that these substances will leach when the plastics come into contact with seawater is greater [16], the substances called plasticizers should be considered in a hazard category and need be reviewed.

5.5. Lubricants

Usually, lubricants are used to minimize adhesion and viscosity of plastic polymers. Internal lubricants can facilitate the production process by providing lubrication at molecular level between the polymer chains [101]. Commonly, they are composed of an oil base accompanied by a variety of additives that confer desirable properties. Lubricants are based in one type of base oil, but in commercial requirements, it usually makes that a mixture are used [102]. n‐Hexadecanoic acid, oleic acid, glycerol tricaprylate, isopropyl myristate, 1‐eicosanol, 2‐hexyl‐1‐decanol, octadecanamide, 4‐methyl‐benzenesulfonamide, 1‐hexacosanol and decanedioic acid, bis(2‐ethylhexyl) ester can be found in plastic debris [16]. The transfer of additives such as lubricants to the medium or to the substances which are in contact with the plastics has been reported previously [103].

5.6. Fuel

Chemicals like pentadactyl ester trichloroacetic acid, 1,10‐[2‐methyl‐2‐(phenylthio) cyclopropenylidene] bisbenzene and 2,4‐dimethyl‐4‐octanol are often found in plastic debris [16]. These substances and others, like hexadecyl ester trichloroacetic acid, have been considered as fuel precursor based on plastic wastes additives, due to the large amount and variety of additives that plastics can contain [63]. Waste plastics are considered a promising source for fuel production because of their high combustion heat and their increasing availability in local communities [104].

5.7. Intermediates

In manufacture of plastics, it is normal to use stabilizers (DEHA or DEHP) and plasticizers that contain intermediate substances like hexanoic acid 2‐ethyl‐hexadecyl ester (HEHA), 2,3‐dihydroxypropyl ester hexadecanoic acid, hexadecanoic acid ethyl ester, behenic alcohol, nonanoic acid, pimaric acid, 3,5‐di‐tert‐butyl‐4‐hydroxyphenyl propionic acid, abietic acid and dehydroabietic acid [16]. HEHA has been classified as belonging to reprotoxic category 3 by Council Directive 67/548/EEC [105].

5.8. Flame retardants

Flame retardants are a group of chemical compounds that are used in plastics with the aim of diminishing the flammability of combustible materials, like synthetic polymers and plastics. To make sure that flame retardants remain in the polymers, these compounds are designed to be stable for many years, which means they will remain in the environment long past the time when the material itself was used [106]. Thus, these compounds can enter aquatic environments via the atmospheric deposition of fine particles, direct discharges of municipal and industrial wastewater effluents, and through run‐off and other human activities [107]. Flame retardants include α, β, γ‐diastereoisomers of hexabromocyclododecane (HBCD), tetrabromobisphenol‐A (TBBP‐A), anti‐ and syn‐isomers of dechlorane plus (DP) and two novel compounds, decabromodiphenylethane (DBDPE) and 2‐bis(2,4,6‐tribromophenoxy) ethane (BTBPE). Among the most widely used flame retards are polybrominated diphenyl ethers, which have been in use since the late 1970s. Polybrominated diphenyl ethers are a class of brominated compounds widely used as flame retardants including in polymers such as low density polyethylene or silicone rubber [45, 108]. Polybrominated diphenyl ethers are very hydrophobic, with log KOW above 5.5 and molecular weights (MW) in the range of 300–1000 g/mol which means that these compounds are likely to have diffusion coefficients significantly lower than those measured for polycyclic aromatic hydrocarbons and polychlorinated biphenyls. This implies that the polymer diffusion coefficients for these plastic additives used as flame retardants need to be taken into account when considering the risk posed by microplastic particle ingestion by marine organisms [109]. Many studies on polybrominated diphenyl ethers [110118] have shown that these compounds are ubiquitous, toxic, persistent and bioaccumulated in the environment. As a result, some flame retardants have been prohibited in the USA and European Union [119, 120], such a penta‐ and octabrominated diphenyl ether. Nevertheless, new compounds have replaced the forbidden polybrominated diphenyl ethers, such as 1,2‐bis(pentabromodiphenyl) ethane, which is used in solid plastics, wire, cable and electronics, high impact polystyrene and thermoplastics [121].

5.9. Monomers and oligomers

Bisphenol A (2,2‐(4,4‐dihydroxydiphenyl) propane) is used as a monomer in polycarbonate, for the production of polycarbonate plastics and epoxy resins. It has been found in samples of PE, PP and acrylate‐styrene, where it is probably used as chain terminator, to finish the polymerization of polymers or as antioxidant for polymers or plasticizers [16]. Bisphenol A is also used to manufacture a great variety of products, including CDs, food can linings, thermal paper, safety helmets, plastic windows, car parts, adhesives, protective coatings, powder paints, and the sheathing of electrical and electronic parts [122]. As a result of its wide usage, bisphenol A is frequently detected in wastewaters [123].

Bisphenol A has been identified as an endocrine disruptor [124], and several studies have demonstrated reproductive, metabolic and neurodevelopmental problems in animals exposed to environmentally relevant levels of this substance [125127]. In addition, an increased risk for cardiovascular disease, altered immune system activity, miscarriages, decreased birthweight at term, metabolic problems and diabetes in adults, breast and prostate cancer, reproductive and sexual dysfunctions and cognitive and behavioural development in young children have been associated with the human exposure to bisphenol A [128134].

It is known that plasticizers may have biological effects even at low concentrations in the ng/L range, especially for molluscs, crustaceans and amphibians [50]. Although it has been argued that one should expect levels of exposure to plastic additives to be low due to the low diffusivities of chemicals like bisphenol A or nonylphenol in plastics [51], as we said above, their bioaccumulation could play an important role, increasing physiological concentrations in the food chain. In an attempt to solve these problems, physicochemical processes for the removal of bisphenol A from wastewaters have been studied [135, 136]. However, possible solutions presented several problems related to the cost of chemicals, the generation of bisphenol A‐containing sludge and the conditions necessary to optimize the bisphenol A elimination process. The most frequently detected metabolic products of the aerobic biodegradation pathway of bisphenol A include 4‐hydroxyacetophenone and 4‐hydroxybenzoic acid [137]. Both bisphenol A and 4‐hydroxybenzoic acids have shown a certain degree of biodegradability [138], and these compounds are not expected to be persistent in an activated sludge system, although the information concerning 4‐hydroxyacetophenone is scarce.

5.10. Others

Degradation products, antifogging, antiblocking, colouring, heat stabilizers, fatty acids and their derivatives have also been found in plastics debris [16]. This heterogeneous group includes 7,9‐di‐tert‐butyl‐1‐oxaspiro(4,5)deca‐6,9‐diene‐2,8‐dione, glycerol 1‐palmitate, (Z)‐13‐docosenamide, 2,3‐dichloro‐1,10‐biphenyl, trans‐13‐docosenamide, di‐tert‐dodecyl disulfide, 1‐hexa‐decanol, 2,4‐bis [2‐(4‐methoxyphenyl‐2‐propyl)] methoxybenzene, oleic acid eicosyl ester, octadecanoic acid, octadecanoic acid 4‐hydroxy‐methyl ester, octadecanoic acid 2‐hydroxy‐1‐(hydroxymethyl)ethyl ester, tridecanoic acid 4,8,12‐trimethyl‐methyl ester, heptanedioic acid 4‐(ethoxycarbonylmethylene)‐diethyl ester and succinic acid [16]. Fatty acids and their esters could originate from several kinds of oils, such as coconut oil (lauric acid) or palm oil (palmitic acid), acids which, along with their esters, are usually used as internal lubricants. Besides, metallic salts of fatty acids are normally used as stabilizers and plasticizers in the production of the plastics.

Other substances can stick or bind to plastics, such as disinfectants, aromatic compounds, soaps used to clean the plastics. In this respect, triclosan (5‐chloro‐2‐[2,4‐dichloro‐phenoxy]‐phenol) is an additive that has been reported to be toxic [139141]. Triclosan is an antimicrobial that is effective against bacteria of the adult oral cavity and skin. It is currently used in antibacterial soaps, deodorants, skin creams, toothpastes and plastics. Triclosan is an ionizable chlorinated biphenyl ether of low water solubility, with a pKa of 8.1, and a vapour pressure of 4 × 10-6 mm Hg [139]. Triclosan readily bioaccumulates within aquatic organisms and has been found to be toxic to fish. In larval fishes, exposure to triclosan disrupts a variety of developmental processes, impairs hatching success, and causes pericardial oedema, having the potential to cause subtle cardiac toxicity [142]. Browne et al. [47] showed that triclosan added to MPs diminished the ability of worms to engineer sediments and caused mortality, each by >55%, while PVC alone made worms >30% more susceptible to oxidative stress. Triclosan persists in water and is difficult to eliminate from wastewaters [143, 144]. The ingestion of MPs by organisms can transfer pollutants and additives (such as triclosan) to their tissues at concentrations sufficient to disrupt ecophysiological functions linked to health and biodiversity. Biomarkers of endocrine disruption found in fish indicated long‐term exposure to estrogenic chemicals in the wastewater [145].

Advertisement

6. Effects on marine fish

The accumulation of microplastic waste could affect the functioning of marine ecosystems. However, the mechanisms by which these effects will be manifested have not been identified. Impacts on biota and marine environmental quality are well documented [146], with damage for the global economy estimated to be in the range of $13 billion per year [147].

Figure 1.

Principal effects of microplastics on fish.

Negative effects include entanglement in plastic wires or nets, or to ingestion, which has been reported in benthic invertebrates, birds, fish, mammals and turtles [148151]. This is especially true for eggs, embryos and larvae of aquatic organisms, which are particularly vulnerable to water‐borne pollutants owing to their limited ability to regulate their internal environment [152]. In particular, the early life stages of fishes are subjected to strong selection forces, driven by high rates of predator‐induced mortality [153, 154]. So, it has been reported that there is a clear overlap between areas with high levels of microplastics pollution and the feeding grounds of fin whales in the Mediterranean Sea, which could mean that fin whales are subjected to a high level of exposure to MPs ingestion during feeding in the areas [155]. The bioaccumulation of MPs and the substances which they could carry seem to be an increasing problem due to MPs which has been detected from little fish species to the top of food web.

The ingestion of the MPs can influence marine animals in different ways (Figure 1). It can affect to the immune system, both chemically (caused by the substances that MPs might contain, absorb or release, which may be toxic) [156] and physically blocking the digestive organs and preventing the animals from feeding [157]. Ecology and behaviour could also be affected.

6.1. Immune system

Interactions between plastic microparticles and aquatic organisms have been reported, and several recent studies have addressed the effects of nanoplastic material on different organisms and their health status. This research suggests that nanoplastics can enter different organisms and may interact with the immune system [158161].

In fish, cellular innate immunity effectors act as one of the first organ defences against various agents, which makes these effectors the possible target for interaction with nanoplastic particles. Neutrophil activation is critical for the host defences, and their function is a valuable tool to assess the health status of individuals and animal populations [162]. So, fish neutrophils can extravasate, migrate chemotactically, degranulate, release neutrophil extracellular traps and phagocytize particulate matter such as bacteria [163]. Hypotheses existed about the interactions between MPs or nanoplastics and the neutrophils until recently, it has been reported that polystyrene and polycarbonate nanoplastic can act as stressors to the innate immune response of fish [164]. Therefore, nanoplastic could potentially interfere with innate immune responses in fish populations by altering organismal defence mechanisms.

In addition, plastic fragments found in the marine habitat have been shown to absorb POPs, so effects on the immune system may be caused by particle toxicity, plastic‐associated chemicals and absorbed environmental chemicals.

6.2. Disrupting effects

Evidence points to the potential role of microplastics as vectors of chemical pollutants, either used as additives during polymer synthesis, or adsorbed directly from seawater [27, 45, 165]. The hydrophobicity of organic xenobiotics and the surfaces of polymers facilitate the adsorption of the chemicals on MPs at concentrations with orders of magnitude higher than those usually detected in seawater [166].

Several of these plastic‐associated chemicals have been linked to endocrine‐disrupting effects in fish. Styrene [167], a monomer of several plastic types including polystyrene, rubber and acrylonitrile–butadiene–styrene, and bisphenol‐A [168] a monomer of polycarbonate, can disrupt the endocrine system function, as mentioned above. In addition, there is evidence that UV stabilizers, phthalates and nonylphenol, additives to plastic, are estrogenic and/or antiandrogenic [169, 170]. Furthermore, chemicals historically known to promote adverse effects in the endocrine system functions, including heavy metals, organochlorine pesticides and petroleum hydrocarbons [171, 172], have been found attached to plastic debris around the world [173, 174].

The ingestion of plastic debris has been documented in fish [175, 176], which may introduce a ‘cocktail’ of endocrine‐disrupting chemicals [47, 150, 177]. Significantly higher concentrations of several polybrominated diphenyl ethers, such as polychlorinated biphenyl congener (PCB#28) and the polycyclic aromatic hydrocarbon chrysene, have been recorded in Japanese medaka (Oryzias latipes) exposed to polyethylene that had been deployed in the marine environment compared to fish exposed to a virgin polyethylene and a control treatment [177].

Fish are useful as sensitive indicators of endocrine‐disrupting chemicals in aquatic habitats, as exposure can result in changes in gonadal growth, gonadal degeneration, sex‐specific gene protein and intersex induction [178]. Finally, recent research showed that ingestion of plastic debris at environmentally relevant concentrations may alter the endocrine system function in adults [179], where the presence of abnormal germ cell proliferation observed may be related to plastic. In this respect, ovary structure protein 1 (OSP1) gene has been proposed as a suitable indicator of the early stages of intersex development and suggested to be a more sensitive early‐warning signal than histopathological observation [180].

6.3. Physiological

It has been shown in various marine organisms that ingestion of MPs occurs in animals with different feeding strategies and may negatively influence both the feeding activity and nutritional value, especially in species which cannot vary their food source [181, 182]. Different studies have pointed to the obstruction and damage of digestive tracts or even animals starving to death caused by stomachs filled with plastic [18]. In addition, MP ingestion by marine biota has been detected in benthic fish species [183, 184], and different sized plastic items were identified in the stomachs of three large pelagic fish in the Mediterranean Sea [185].

In a study made in Spanish coastal waters and which constitutes the first report of MPs ingestion by demersal fishes, red mullets (Mullus barbatus) from Barcelona presented the highest abundance of microplastics, followed by dogfish (Scyliorhinus canicula) from the Cantabrian coast and the Gulf of Cadiz, whereas dogfish from the Galician coast presented the lowest levels [186]. In agreement with previous studies, the detected MPs were mostly fibres (71%) [174, 184, 187], and the most frequent colour was black (51%) (Table 5).

Because of their small size, MPs may be ingested by marine organisms, regardless of their feeding mechanisms, and may enter their circulatory system and accumulate in different types of tissues, as has been proven in laboratory experiments [182]. These reported data, along with the fact that MPs serve as dispersal vectors for invasive species [188] and the toxic and bioaccumulative substances bound to the plastics [149], together with the research that indicates that MPs may have the ability to enter and disseminate though the marine food web [189, 190], suggest grave ecological implications of microplastics across the food web.

Form  Percentage (%) 
Fibre  71.0 
Sphere  24.2 
Film  3.2 
Fragment  1.6 

Table 5.

Types of plastics found in fish and their relative abundance in Spanish coastal waters [188].

6.4. Behaviour

Behaviour is a crucial determinant for essential parameters such as overall health, growth, reproduction and survival [191]. During the life cycle of fish, a critical point is the early stage of development. Survival depends, in many cases, on the capacity of the organism to evade predators. An innate ability to detect and act accordingly is therefore vital [153, 154, 192].

In this regard, it has been suggest that olfactory sense in fish larvae could suffer damage mediated by an immunological response produced by the pollutant from microplastics. Lönnstedt and Eklöv [193] found that not only was crucial behaviour, such as activity and feeding, affected by microplastics, but that innate responses to olfactory threat cues were also impaired. Such a loss of predator avoidance behaviour greatly increased predator‐induced mortality rates of larvae. Finally, survival of fishes could be seriously affected by the presence of MPs, with their significant impact on the life cycle of the fish.

Advertisement

7. Conclusion

Microplastics in the aquatic environment have been demonstrated to be a significant problem. The great amount of research on this topic, as well as the quantity of the results that describe the problem of MPs and their effects on fishes and aquatic life, have thrown some light on this issue. Among the effects that MPs have are stress, intestinal obstruction and the alteration of health, while further studies are in progress to ascertain the full potential risks of MPs in aquatic organisms with special attention paid to fish. A huge number of substances are added to plastics, which can bioaccumulate throughout the trophic chain. Besides the problems that MPs represent for marine life in general, the MPs could begin act as disruptors of the welfare and health of fishes, both wild and cultivated. This is clearly a growing problem not only for the environment but also for human health. For these reasons, further efforts are needed to know the exact effects that microplastics, and their constitutive and adsorbed contaminants, may have on aquatic environments.

Advertisement

Acknowledgments

Financial support by grants PCIN‐2015‐187‐C03‐02 (MINECO, JPIOceans: Microplastics, EPHEMARE) and 19883/GERM/15 (Fundación Séneca de la Región de Murcia, Spain) is gratefully acknowledged.

References

  1. 1. Plastics: The Facts 2015: An analysis of European latest plastics production, demand and waste data. [Internet]. 2015. Available from: http://www.corepla.it/documenti/5f2fa32a‐7081‐416f‐8bac‐2efff3ff2fbd/Plastics+TheFacts+2015.pdf [Accessed: 2016‐06‐29]
  2. 2. Eubeler JP, Bernhard M, Knepper TP. Environmental biodegradation of synthetic polymers II. Biodegradation of different polymer groups. TrAC Trends Anal Chem. 2010;29:84–100
  3. 3. Barnes DKA, Galgani F, Thompson RC, Barlaz M. Accumulation and fragmentation of plastic debris in global environments. Philos Trans R Soc Lond B Biol Sci. 2009;364:1985–1998. doi:10.1098/rstb.2008.0205
  4. 4. Thompson RC, Olsen Y, Mitchell RP, Davis A, Rowland SJ, John AWG, et al. Lost at sea: where is all the plastic? Science. 2004;304:838. doi:10.1126/science.1094559
  5. 5. Andrady AL. Microplastics in the marine environment. Mar Pollut Bull. 2011;62:1596–1605. doi:10.1016/j.marpolbul.2011.05.030
  6. 6. Gregory MR, Ryan PG. Pelagic plastics and other seaborne persistent synthetic debris: a review of southern hemisphere perspectives. In: Coe JM, Rogers DB, editors. New York: Springer Series on Environmental Management; 1997. p. 49–66
  7. 7. Zarfl C, Matthies M. Are marine plastic particles transport vectors for organic pollutants to the Arctic? Mar Pollut Bull. 2010;60:1810–1814. doi:10.1016/j.marpolbul.2010.05.026
  8. 8. Roy PK, Hakkarainen M, Varma IK, Albertsson A‐C. Degradable polyethylene: fantasy or reality. Environ Sci Technol. 2011;45:4217–4227. doi:10.1021/es104042f
  9. 9. Gregory MR, Andrady AL, editors. Plastics in the marine environment, in plastics and the environment. Wiley, A. L. Andrad, Inc., Hoboken, NJ, USA. 2003. doi:10.1002/0471721557.ch10
  10. 10. Frankel EN. In search of better methods to evaluate natural antioxidants and oxidative stability of food lipids. Trends Food Sci Technol. 1993;4:220–225
  11. 11. Betts K. Why small plastic particles may pose a big problem in the oceans. Environ Sci Technol. 2008;42:8995
  12. 12. Moore CJ. Synthetic polymers in the marine environment: a rapidly increasing, long‐term threat. Environ Res. 2008;108:131–139
  13. 13. Koelmans AA, Besseling E, Shim W. Nanoplastics in the aquatic environment. Critical review. In: Bergmann M, Gutow L, Klages M, editors. Marine Anthropog Litter. 2015;3:325–340. doi: 10.1007/978-3-319-16510-3_12
  14. 14. Cozar A, Echevarria F, Gonzalez‐Gordillo JI, Irigoien X, Ubeda B, Hernandez‐Leon S, et al. Plastic debris in the open ocean. Proc Natl Acad Sci. 2014;111:10239–10244. doi:10.1073/pnas.1314705111
  15. 15. Andrady AL, Neal MA, Andersen ME, Clewell HJ, Tan Y‐M, Butenhoff JL, et al. Applications and societal benefits of plastics. Philos Trans R Soc Lond B Biol Sci. 2009;364:1977–1984. doi:10.1098/rstb.2008.0304
  16. 16. Rani M, Shim WJ, Han GM, Jang M, Al‐Odaini NA, Song YK, et al. Qualitative analysis of additives in plastic marine debris and its new products. Arch Environ Contam Toxicol. 2015;69:352–66. doi:10.1007/s00244‐015‐0224‐x
  17. 17. Hidalgo‐Ruz V, Gutow L, Thompson RC, Thiel M. Microplastics in the marine environment: a review of the methods used for identification and quantification. Environ Sci Technol. 2012;46:3060–3075. doi:10.1021/es2031505
  18. 18. Kühn S, Bravo Rebolledo EL, van Franeker JA. Deleterious effects of litter on marine life. Mar. Anthropog. Litter, Cham: Springer International Publishing; 2015. 75–116 p. doi:10.1007/978‐3‐319‐16510‐3_4
  19. 19. Browne MA, Crump P, Niven SJ, Teuten EL, Tonkin A, Galloway T, et al. Accumulations of microplastic on shorelines worldwide: sources and sinks. Environ Sci Technol. 2011;45(21):9175–9179. doi:10.1021/es201811s
  20. 20. Li WC, Tse HF, Fok L. Plastic waste in the marine environment: a review of sources, occurrence and effects. Sci Total Environ. 2016;566:333–349. doi:10.1016/j.scitotenv.2016.05.084
  21. 21. Yonkos LT, Friedel EA, Perez‐Reyes AC, Ghosal S, Arthur CD. Microplastics in four estuarine rivers in the Chesapeake Bay, U.S.A. Environ Sci Technol. 2014;48:14195–14202. doi:10.1021/es5036317
  22. 22. Castañeda R, Avlijas S. Microplastic pollution in St. Lawrence River sediments. Can J Fish Aquat Sci. 2014;5:1–5
  23. 23. Mani T, Hauk A, Walter U, Burkhardt‐Holm P. Microplastics profile along the Rhine River. Sci Rep. 2015;5:17988. doi:10.1038/srep17988
  24. 24. Lechner A, Keckeis H, Lumesberger‐Loisl F, Zens B, Krusch R, Tritthart M, et al. The Danube so colourful: a potpourri of plastic litter outnumbers fish larvae in Europe’s second largest river. Environ Pollut. 2014;188:177–181. doi:10.1016/j.envpol.2014.02.006
  25. 25. Sundt P, Schulze P‐E, Syversen F. Sources of microplastics‐pollution to the marine environment, Report M‐321‐2015. 2014
  26. 26. Magnusson K, Noren F. Screening of microplastic particles in and down‐stream a wastewater treatment plant. 2014;55:1–22
  27. 27. Engler RE. The complex interaction between marine debris and toxic chemicals in the ocean. Environ Sci Technol. 2012;46:12302–12315. doi:10.1021/es3027105
  28. 28. Thompson RC, Moore CJ, vom Saal FS, Swan SH. Plastics, the environment and human health: current consensus and future trends. Philos Trans R Soc Lond B Biol Sci. 2009;364:2153–2166. doi:10.1098/rstb.2009.0053
  29. 29. Driedger AGJ, Dürr HH, Mitchell K, Van Cappellen P. Plastic debris in the Laurentian Great Lakes: a review. J Great Lakes Res. 2015;41:9–19. doi:10.1016/j.jglr.2014.12.020
  30. 30. Duis K, Coors A. Microplastics in the aquatic and terrestrial environment: sources (with a specific focus on personal care products), fate and effects. Environ Sci Eur. 2016;16(1):273. doi:10.1186/s12302‐015‐0069‐y
  31. 31. Lagarde F, Olivier O, Zanella M, Daniel P, Hiard S, Caruso A. Microplastic interactions with freshwater microalgae: hetero‐aggregation and changes in plastic density appear strongly dependent on polymer type. Environ Pollut. 2016;215:331–339. doi:10.1016/j.envpol.2016.05.006
  32. 32. Long M, Moriceau B, Gallinari M, Lambert C, Huvet A, Raffray J, et al. Interactions between microplastics and phytoplankton aggregates: impact on their respective fates. Mar Chem. 2015;175:39–46. doi:10.1016/j.marchem.2015.04.003
  33. 33. Eriksen M, Maximenko N, Thiel M, Cummins A, Lattin G, Wilson S, et al. Plastic pollution in the South Pacific subtropical gyre. Mar Pollut Bull. 2013;68:71–76. doi:10.1016/j.marpolbul.2012.12.021
  34. 34. Goldstein MC, Titmus AJ, Ford M, Derraik J, Barnes D, Galgani F, et al. Scales of spatial heterogeneity of plastic marine debris in the Northeast Pacific Ocean. PLoS One. 2013;8(11):e80020. doi:10.1371/journal.pone.0080020
  35. 35. Shaw DG, Day RH. Colour‐ and form‐dependent loss of plastic micro‐debris from the North Pacific Ocean. Mar Pollut Bull. 1994;28:39–43. doi:10.1016/0025‐326X(94)90184‐8
  36. 36. Doyle MJ, Watson W, Bowlin NM, Sheavly SB. Plastic particles in coastal pelagic ecosystems of the Northeast Pacific ocean. Mar Environ Res. 2011;71:41–52. doi:10.1016/j.marenvres.2010.10.001
  37. 37. Desforges J‐PW, Galbraith M, Dangerfield N, Ross PS. Widespread distribution of microplastics in subsurface seawater in the NE Pacific Ocean. Mar Pollut Bull. 2014;79:94–99. doi:10.1016/j.marpolbul.2013.12.035
  38. 38. Lusher AL, Burke A, O’Connor I, Officer R. Microplastic pollution in the Northeast Atlantic Ocean: validated and opportunistic sampling. Mar Pollut Bull. 2014;88:325–333. doi:10.1016/j.marpolbul.2014.08.023
  39. 39. Reddy MS, Shaik Basha, Adimurthy S, Ramachandraiah G. Description of the small plastics fragments in marine sediments along the Alang‐Sosiya ship‐breaking yard, India. Estuar Coast Shelf Sci. 2006;68:656–660. doi:10.1016/j.ecss.2006.03.018
  40. 40. Collignon A, Hecq J‐H, Glagani F, Voisin P, Collard F, Goffart A. Neustonic microplastic and zooplankton in the North Western Mediterranean Sea. Mar Pollut Bull. 2012;64:861–864. doi:10.1016/j.marpolbul.2012.01.011
  41. 41. Fossi MC, Panti C, Guerranti C, Coppola D, Giannetti M, Marsili L, et al. Are baleen whales exposed to the threat of microplastics? A case study of the Mediterranean fin whale (Balaenoptera physalus). Mar Pollut Bull. 2012;64:2374–2379. doi:10.1016/j.marpolbul.2012.08.013
  42. 42. Mascia L. The role of additives in plastics. M PolymSci Pol Lett. 1975;13 (10):632. doi: 10.1002/pol.1975.130131020
  43. 43. Koelmans AA, Besseling E, Foekema EM. Leaching of plastic additives to marine organisms. Environ Pollut. 2014;187:49–54. doi:10.1016/j.envpol.2013.12.013
  44. 44. Gouin T, Roche N, Lohmann R, Hodges G. A thermodynamic approach for assessing the environmental exposure of chemicals absorbed to microplastic. Environ Sci Technol. 2011;45:1466–1472. doi:10.1021/es1032025
  45. 45. Teuten EL, Saquing JM, Knappe DRU, Barlaz MA, Jonsson S, Björn A, et al. Transport and release of chemicals from plastics to the environment and to wildlife. Philos Trans R Soc Lond B Biol Sci. 2009;364:2027–2045. doi:10.1098/rstb.2008.0284
  46. 46. Hammer J, Kraak MHS, Parsons JR. Plastics in the marine environment: the dark side of a modern gift. Rev Environ Contam Toxicol. 2012;220:1–44. doi:10.1007/978‐1‐4614‐3414‐6_1
  47. 47. Browne MA, Niven SJ, Galloway TS, Rowland SJ, Thompson RC. Microplastic moves pollutants and additives to worms, reducing functions linked to health and biodiversity. Curr Biol. 2013;23:2388–2392. doi:10.1016/j.cub.2013.10.012
  48. 48. Koelmans AA, Besseling E, Wegner A, Foekema EM. Plastic as a carrier of POPs to aquatic organisms: a model analysis. Environ Sci Technol. 2013;47:7812–7820. doi:10.1021/es401169n
  49. 49. Koelmans AA, Besseling E, Wegner A, Foekema EM. Correction to plastic as a carrier of POPs to aquatic organisms. A model analysis. Environ Sci Technol. 2013;47:8992–8993
  50. 50. Oehlmann J, Schulte‐Oehlmann U, Kloas W, Jagnytsch O, Lutz I, Kusk KO, et al. A critical analysis of the biological impacts of plasticizers on wildlife. Philos Trans R Soc Lond B Biol Sci. 2009;364:2047–2062. doi:10.1098/rstb.2008.0242
  51. 51. Berens AR. Predicting the migration of endocrine disrupters from rigid plastics. Polym Eng Sci. 1997;37:391–395. doi:10.1002/pen.11681
  52. 52. Lee C‐C, Jiang L‐Y, Kuo Y‐L, Chen C‐Y, Hsieh C‐Y, Hung C‐F, et al. Characteristics of nonylphenol and bisphenol A accumulation by fish and implications for ecological and human health. Sci Total Environ. 2015;502:417–425. doi:10.1016/j.scitotenv.2014.09.042
  53. 53. Staples CA, Parkerton TF, Peterson DR. A risk assessment of selected phthalate esters in North American and Western European surface waters. Chemosphere. 2000;40:885–891. doi:10.1016/S0045‐6535(99)00315‐X
  54. 54. Santa Cruz Biotechnology, Inc. [Internet]. 2007. Available from: http://www.scbt.com. [Accessed: 2016‐07‐01]
  55. 55. European chemical agency [Internet]. 2007. Available from: http://echa.europa.eu/es. [Accessed: 2016‐07‐01]
  56. 56. National Library of Medicine. PUBMED [Internet]. 2000. Available from: http://pubchem.ncbi.nlm.nih.gov. [Accessed: 2016‐07‐01]
  57. 57. ChemSpider. Royal Society of Chemistry [Internet]. 2015. Available from: http://www.chemspider.com. [Accessed: 2016‐07‐01]
  58. 58. Guerra P, Eljarrat E, Barceló D. Determination of halogenated flame retardants by liquid chromatography coupled to mass spectrometry. TrAC Trends Anal Chem. 2011;30:842–855. doi:10.1016/j.trac.2011.01.018
  59. 59. Anderson DR, Lusty EB. Acute toxicity and bioaccumulation of chloroform to four species of freshwater fish. Batelle Pacific Northwest Laboratories, US Nuclear Regulatory Commission, Richland, Washington, Report No. CR‐0893. 1980
  60. 60. Chain EFSA Panel on Contaminants in the Food. Scientific opinion on polybrominated biphenyls (PBBs) in food. Eur Food Saf Auth. 2010;8:1–151. doi:10.2903/j.efsa.2010.1789
  61. 61. Palm A, Cousins IT, Mackay D, Tysklind M, Metcalfe C, Alaee M. Assessing the environmental fate of chemicals of emerging concern: a case study of the polybrominated diphenyl ethers. Environ Pollut. 2002;117:195–213
  62. 62. Toxicological profile for polybrominated biphenyls and polybrominated diphenyl ethers. ATSDR, Atlanta, GA. Agency Toxic Subst Dis Regist. [Internet]. 2004. Available from: http://www.atsdr.cdc.gov/toxprofiles/tp.asp?id=529&tid=94. [Accessed: 2016‐07‐01]
  63. 63. Rashid MM, Sarker M. Waste polyethylene terephthalate (PETE) and polystyrene (PS) into fuel. Int J Sci Technol Res. 2013;2:176–189
  64. 64. Rogan WJ, Gladen BC. Neurotoxicology of PCBs and related compounds. Neurotoxicology. 1992;13:27–35
  65. 65. Evangelista de Duffard AM, Duffard R. Behavioral toxicology, risk assessment, and chlorinated hydrocarbons. Environ Health Perspect. 1996;104:353–360
  66. 66. Dornath PJ. Analysis of chemical leaching from common consumer plastic bottles under high stress conditions [thesis] Oregon State University. University Honors College, USA; 2010
  67. 67. Kawamura Y, Ogawa Y, Nishimura T, Kikuchi Y, Nishikawa J, Nishihara T, et al. Estrogenic activities of UV stabilizers used in food contact plastics and benzophenone derivatives tested by the Yeast two‐hybrid assay. J Heal Sci. 2003;49:205–212
  68. 68. Morohoshi K, Yamamoto H, Kamata R, Shiraishi F, Koda T, Morita M. Estrogenic activity of 37 components of commercial sunscreen lotions evaluated by in vitro assays. Toxicol In Vitro. 2005;19:457–469. doi:10.1016/j.tiv.2005.01.004
  69. 69. Fent K, Kunz PY, Gomez E. UV Filters in the aquatic environment induce hormonal effects and affect fertility and reproduction in fish. Chim Int J Chem. 2008;62:368–375. doi:10.2533/chimia.2008.368
  70. 70. Kim J‐W, Chang K‐H, Isobe T, Tanabe S. Acute toxicity of benzotriazole ultraviolet stabilizers on freshwater crustacean (Daphnia pulex). J Toxicol Sci. 2011;36:247–251
  71. 71. Nakata H, Shinohara R, Murata S, Watanabe M. Detection of benzotriazole UV stabilizers in the blubber of marine mammals by gas chromatography‐high resolution mass spectrometry (GC‐HRMS). J Environ Monit. 2010;12:2088–2092. doi:10.1039/c0em00170h
  72. 72. Kameda Y, Kimura K, Miyazaki M. Occurrence and profiles of organic sun‐blocking agents in surface waters and sediments in Japanese rivers and lakes. Environ Pollut. 2011;159:1570–1576. doi:10.1016/j.envpol.2011.02.055
  73. 73. Zhang Z, Ren N, Li Y‐F, Kunisue T, Gao D, Kannan K. Determination of benzotriazole and benzophenone UV filters in sediment and sewage sludge. Environ Sci Technol. 2011;45:3909–3916. doi:10.1021/es2004057
  74. 74. Wick A, Jacobs B, Kunkel U, Heininger P, Ternes TA. Benzotriazole UV stabilizers in sediments, suspended particulate matter and fish of German rivers: new insights into occurrence, time trends and persistency. Environ Pollut. 2016;212:401–412. doi:10.1016/j.envpol.2016.01.024
  75. 75. Gago‐Ferrero P, Díaz‐Cruz MS, Barceló D. Multi‐residue method for trace level determination of UV filters in fish based on pressurized liquid extraction and liquid chromatography‐quadrupole‐linear ion trap‐mass spectrometry. J Chromatogr A. 2013;1286:93–101. doi:10.1016/j.chroma.2013.02.056
  76. 76. Díaz‐Cruz MS, Gago‐Ferrero P, Llorca M, Barceló D. Analysis of UV filters in tap water and other clean waters in Spain. Anal Bioanal Chem. 2012;402:2325–2333. doi:10.1007/s00216‐011‐5560‐8
  77. 77. Pezo D, Salafranca J, Nerín C. Development of an automatic multiple dynamic hollow fibre liquid‐phase microextraction procedure for specific migration analysis of new active food packagings containing essential oils. J Chromatogr A. 2007;1174:85–94. doi:10.1016/j.chroma.2007.08.033
  78. 78. Lau OW, Wong SK. Contamination in food from packaging material. J Chromatogr A. 2000;882:255–270
  79. 79. Heiserman WM, Can SZ, Walker RA, Begley TH, Limm W. Interfacial behavior of common food contact polymer additives. J Colloid Interface Sci. 2007;311:587–594. doi:10.1016/j.jcis.2007.03.047
  80. 80. Bodai Z, Szabó BS, Novák M, Hámori S, Nyiri Z, Rikker T, et al. Analysis of potential migrants from plastic materials in milk by liquid chromatography‐mass spectrometry with liquid‐liquid extraction and low‐temperature purification. J Agric Food Chem. 2014;62:10028–10037. doi:10.1021/jf503110v
  81. 81. Farajzadeh MA, Bahram M, Jönsson JA. Dispersive liquid‐liquid microextraction followed by high‐performance liquid chromatography‐diode array detection as an efficient and sensitive technique for determination of antioxidants. Anal Chim Acta. 2007;591:69–79. doi:10.1016/j.aca.2007.03.040
  82. 82. Sobhi HR, Kashtiaray A, Farahani H, Farahani MR. Quantitation of antioxidants in water samples using ionic liquid dispersive liquid‐liquid microextraction followed by high‐performance liquid chromatography‐ultraviolet detection. J Sep Sci. 2011;34:77–82. doi:10.1002/jssc.201000526
  83. 83. Nerín C, Salafranca J, Cacho J, Rubio C. Separation of polymer and on‐line determination of several antioxidants and UV stabilizers by coupling size‐exclusion and normal‐phase high‐performance liquid chromatography columns. J Chromatogr A. 1995;690:230–236. doi:10.1016/0021‐9673(94)01132‐X
  84. 84. Lin Q‐B, Li B, Song H, Li X‐M. Determination of 7 antioxidants, 8 ultraviolet absorbents, and 2 fire retardants in plastic food package by ultrasonic extraction and ultra performance liquid chromatography. J Liq Chromatogr Relat Technol. 2011;53:1026–1035. doi:10.1093/chromsci/bmu159
  85. 85. Pivnenko K, Eriksen MK, Martín‐Fernández JA, Eriksson E, Astrup TF. Recycling of plastic waste: presence of phthalates in plastics from households and industry. Waste Manag. 2016;54:44–52. doi:10.1016/j.wasman.2016.05.014
  86. 86. He M, Yang C, Geng R, Zhao X, Hong L, Piao X, et al. Monitoring of phthalates in foodstuffs using gas purge microsyringe extraction coupled with GC‐MS. Anal Chim Acta. 2015;879:63–68. doi:10.1016/j.aca.2015.02.066
  87. 87. Phuong NN, Zalouk‐Vergnoux A, Poirier L, Kamari A, Châtel A, Mouneyrac C, et al. Is there any consistency between the microplastics found in the field and those used in laboratory experiments? Environ Pollut. 2016;211:111–123. doi:10.1016/j.envpol.2015.12.035
  88. 88. Jurewicz J, Hanke W. Exposure to phthalates: reproductive outcome and children health. A review of epidemiological studies. Int J Occup Med Environ Health. 2011;24:115‐141. doi:10.2478/s13382‐011‐0022‐2
  89. 89. Braun JM, Sathyanarayana S, Hauser R. Phthalate exposure and children’s health. Curr Opin Pediatr. 2013;25:247–254. doi:10.1097/MOP.0b013e32835e1eb6
  90. 90. Just AC, Whyatt RM, Perzanowski MS, Calafat AM, Perera FP, Goldstein IF, et al. Prenatal exposure to butylbenzyl phthalate and early eczema in an urban cohort. Environ Health Perspect. 2012;120:1475–1480. doi:10.1289/ehp.1104544
  91. 91. Gascon M, Casas M, Morales E, Valvi D, Ballesteros‐Gómez A, Luque N, et al. Prenatal exposure to bisphenol A and phthalates and childhood respiratory tract infections and allergy. J Allergy Clin Immunol. 2015;135:370–378. doi:10.1016/j.jaci.2014.09.030
  92. 92. Whyatt RM, Perzanowski MS, Just AC, Rundle AG, Donohue KM, Calafat AM, et al. Asthma in inner‐city children at 5–11 years of age and prenatal exposure to phthalates: the Columbia center for children’s environmental health cohort. Environ Health Perspect. 2014;122:1141–1146. doi:10.1289/ehp.1307670
  93. 93. Ku HY, Su PH, Wen HJ, Sun HL, Wang CJ, Chen HY, et al. Prenatal and postnatal exposure to phthalate esters and asthma: a 9‐year follow‐up study of a Taiwanese birth cohort. PLoS One. 2015;10:e0123309. doi:10.1371/journal.pone.0123309
  94. 94. Vrijheid M, Casas M, Gascon M, Valvi D, Nieuwenhuijsen M. Environmental pollutants and child health—A review of recent concerns. Int J Hyg Environ Health. 2016;219:331–342. doi:10.1016/j.ijheh.2016.05.001
  95. 95. Minatoya M, Naka Jima S, Sasaki S, Araki A, Miyashita C, Ikeno T, et al. Effects of prenatal phthalate exposure on thyroid hormone levels, mental and psychomotor development of infants: the Hokkaido study on environment and children’s health. Sci Total Environ. 2016;565:1037–1043. doi:10.1016/j.scitotenv.2016.05.098
  96. 96. Yi H, Gu H, Zhou T, Chen Y, Wang G, Jin Y, et al. A pilot study on association between phthalate exposure and missed miscarriage. Eur Rev Med Pharmacol Sci. 2016;20:1894–902
  97. 97. Mráz M, Svačina Š, Kotrlíková E, Piecha R, Vrbík K, Pavloušková J, et al. Potential sources of phthalates and bisphenol A and their significance in the development of metabolic diseases. Casopís Lékaru Ceských. 2016;155:11–15
  98. 98. Jobling S, Reynolds T, White R, Parker MG, Sumpter JP. A variety of environmentally persistent chemicals, including some phthalate plasticizers, are weakly estrogenic. Environ Health Perspect. 1995;103:582–587
  99. 99. Duty SM, Silva MJ, Barr DB, Brock JW, Ryan L, Chen Z, et al. Phthalate exposure and human semen parameters. Epidemiology. 2003;14:269–277
  100. 100. Hauser R, Calafat AM. Phthalates and human health. Occup Environ Med. 2005;62:806–818. doi:10.1136/oem.2004.017590
  101. 101. Yarimitsu S, Moro T, Kyomoto M, Watanabe K, Tanaka S, Ishihara K, et al. Influences of dehydration and rehydration on the lubrication properties of phospholipid polymer‐grafted cross‐linked polyethylene. Proc Inst Mech Eng H. 2015;229:506–514. doi:10.1177/0954411915588969
  102. 102. Pomelli C, Ghilardi T, Chiappe C, de Angelis A, Calemma V. Alkylation of methyl linoleate with propene in ionic liquids in the presence of metal salts. Molecules. 2015;20:21840–21853. doi:10.3390/molecules201219805
  103. 103. Fordham PJ, Gramshaw JW, Crews HM, Castle L. Element residues in food contact plastics and their migration into food simulants, measured by inductively‐coupled plasma‐mass spectrometry. Food Addit Contam. 1995;12:651–669. doi:10.1080/02652039509374354
  104. 104. Kumar PS, Sankaranarayanan G. Investigation on environmental factors of waste plastics into oil and its emulsion to control the emission in DI diesel engine. Ecotoxicol Environ Saf. 2016. S0147‐6513:30021‐30025. doi:10.1016/j.ecoenv.2016.01.021
  105. 105. Council Directive 67/548/EEC of 27 June 1967 on the approximation of laws, regulations and administrative provisions relating to the classification, packaging and labelling of dangerous substance. English special edition: Series I. 1967. p. 234–256
  106. 106. Eljarrat E, Barceló D, editors. The handbook of environmental chemistry. ed Berlin Heidelberg: Springer-Verlag; 2011. 290 p. doi:10.1016/0143‐1471(82)90111‐8
  107. 107. Al‐Odaini NA, Yim UH, Kim NS, Shim WJ, Hong SH. Isotopic dilution determination of emerging flame retardants in marine sediments by HPLC‐APCI‐MS/MS. Anal Methods. 2013;5:1771. doi:10.1039/c3ay25963c
  108. 108. Reynier A, Dole P, Humbel S, Feigenbaum A. Diffusion coefficients of additives in polymers. I. Correlation with geometric parameters. J Appl Polym Sci. 2001;82:2422–2433. doi:10.1002/APP.2093
  109. 109. Narváez Valderrama JF, Baek K, Molina FJ, Allan IJ. Implications of observed PBDE diffusion coefficients in low density polyethylene and silicone rubber. Environ Sci Process Impacts. 2016;18:87–94. doi:10.1039/c5em00507h
  110. 110. Zhu L, Hites RA. Brominated flame retardants in tree bark from North America. Environ Sci Technol. 2006;40:3711–3716
  111. 111. Kim GB, Stapleton HM. PBDEs, methoxylated PBDEs and HBCDs in Japanese common squid (Todarodes pacificus) from Korean offshore waters. Mar Pollut Bull. 2010;60:935–940. doi:10.1016/j.marpolbul.2010.03.025
  112. 112. Hu G, Xu Z, Dai J, Mai B, Cao H, Wang J, et al. Distribution of polybrominated diphenyl ethers and decabromodiphenylethane in surface sediments from Fuhe River and Baiyangdian Lake, North China. J Environ Sci (China). 2010;22:1833–1839
  113. 113. Hong SH, Kannan N, Jin Y, Won JH, Han GM, Shim WJ. Temporal trend, spatial distribution, and terrestrial sources of PBDEs and PCBs in Masan Bay, Korea. Mar Pollut Bull. 2010;60:1836–1841. doi:10.1016/j.marpolbul.2010.05.023
  114. 114. Boer J de, Allchin C, Law R, Zegers B, Boon JP. Method for the analysis of polybrominated diphenylethers in sediments and biota. Trends Anal Chem. 2001;20:591–599
  115. 115. Sellstrom U, B. Jansson. Analysis of tetrabromobisphenol A in a product and environmental samples. Chemosphere. 1995;31:3085–3092
  116. 116. Sjödin A, Carlsson H, Thuresson K, Sjölin S, Bergman A, Ostman C. Flame retardants in indoor air at an electronics recycling plant and at other work environments. Environ Sci Technol. 2001;35:448–454
  117. 117. Oberg K, Warman K, Oberg T. Distribution and levels of brominated flame retardants in sewage sludge. Chemosphere. 2002;48:805–809
  118. 118. Kierkegaard A, Björklund J, Fridén U. Identification of the flame retardant decabromodiphenyl ethane in the environment. Environ Sci Technol. 2004;38:3247–3253
  119. 119. California State Assembly, Assembly Bill no. 302, California State. 2003
  120. 120. Viganò L, Mascolo G, Roscioli C. Emerging and priority contaminants with endocrine active potentials in sediments and fish from the River Po (Italy). Environ Sci Pollut R. 2015;22:14050–14066. doi:10.1007/s11356‐015‐4388‐8
  121. 121. Covaci A, Harrad S, Abdallah MA‐E, Ali N, Law RJ, Herzke D, et al. Novel brominated flame retardants: a review of their analysis, environmental fate and behaviour. Environ Int. 2011;37:532–556. doi:10.1016/j.envint.2010.11.007
  122. 122. Staples CA, Dorn PB, Klecka GM, O’Block ST, Harris LR. A review of the environmental fate, effects, and exposures of bisphenol A. Chemosphere. 1998;36:2149–2173
  123. 123. Melcer H, Klecka G. Treatment of wastewaters containing bisphenol A: state of the science review. Water Environ Res. 2011;83:650–666
  124. 124. Omoike A, Wacker T, Navidonski M. Biodegradation of bisphenol A by Heliscus lugdunensis, a naturally occurring hyphomycete in freshwater environments. Chemosphere. 2013;91:1643–1647. doi:10.1016/j.chemosphere.2012.12.045
  125. 125. Salian S, Doshi T, Vanage G. Perinatal exposure of rats to Bisphenol A affects the fertility of male offspring. Life Sci. 2009;85:742–52. doi:10.1016/j.lfs.2009.10.004
  126. 126. Wei J, Lin Y, Li Y, Ying C, Chen J, Song L, et al. Perinatal exposure to bisphenol A at reference dose predisposes offspring to metabolic syndrome in adult rats on a high‐fat diet. Endocrinology. 2011;152:3049–3061. doi:10.1210/en.2011‐0045
  127. 127. Wolstenholme JT, Taylor JA, Shetty SRJ, Edwards M, Connelly JJ, Rissman EF. Gestational exposure to low dose bisphenol A alters social behavior in juvenile mice. PLoS One. 2011;6:e25448. doi:10.1371/journal.pone.0025448
  128. 128. Braun JM, Kalkbrenner AE, Calafat AM, Yolton K, Ye X, Dietrich KN, et al. Impact of early‐life bisphenol A exposure on behavior and executive function in children. Pediatrics. 2011;128:873–882. doi:10.1542/peds.2011‐1335
  129. 129. Braun JM, Yolton K, Dietrich KN, Hornung R, Ye X, Calafat AM, et al. Prenatal bisphenol A exposure and early childhood behavior. Environ Health Perspect. 2009;117:1945–1952. doi:10.1289/ehp.0900979
  130. 130. Lang IA, Galloway TS, Scarlett A, Henley WE, Depledge M, Wallace RB, et al. Association of urinary bisphenol A concentration with medical disorders and laboratory abnormalities in adults. JAMA. 2008;300:1303–1310. doi:10.1001/jama.300.11.1303
  131. 131. Clayton EMR, Todd M, Dowd JB, Aiello AE. The impact of bisphenol A and triclosan on immune parameters in the U.S. population, NHANES 2003‐2006. Environ Health Perspect. 2011;119:390–396. doi:10.1289/ehp.1002883
  132. 132. Li D, Zhou Z, Qing D, He Y, Wu T, Miao M, et al. Occupational exposure to bisphenol‐A (BPA) and the risk of self‐reported male sexual dysfunction. Hum Reprod. 2010;25:519–527. doi:10.1093/humrep/dep381
  133. 133. Miao M, Yuan W, Zhu G, He X, Li D‐K. In utero exposure to bisphenol‐A and its effect on birth weight of offspring. Reprod Toxicol. 2011;32:64–68. doi:10.1016/j.reprotox.2011.03.002
  134. 134. Sugiura‐Ogasawara M, Ozaki Y, Sonta S, Makino T, Suzumori K. Exposure to bisphenol A is associated with recurrent miscarriage. Hum Reprod. 2005;20:2325–2329. doi:10.1093/humrep/deh888
  135. 135. Zeng G, Zhang C, Huang G, Yu J, Wang Q, Li J, et al. Adsorption behavior of bisphenol A on sediments in Xiangjiang River, Central‐south China. Chemosphere. 2006;65:1490–9. doi:10.1016/j.chemosphere.2006.04.013
  136. 136. Xiaoying M, Guangming Z, Chang Z, Zisong W, Jian Y, Jianbing L, et al. Characteristics of BPA removal from water by PACl‐Al13 in coagulation process. J Colloid Interface Sci. 2009;337:408–413. doi:10.1016/j.jcis.2009.05.052
  137. 137. Gao J, Ellis LBM, Wackett LP. The university of Minnesota biocatalysis/biodegradation database: improving public access. Nucleic Acids Res. 2010;38:488–491. doi:10.1093/nar/gkp771
  138. 138. Stasinakis AS, Petalas A V, Mamais D, Thomaidis NS. Application of the OECD 301F respirometric test for the biodegradability assessment of various potential endocrine disrupting chemicals. Bioresour Technol. 2008;99:3458–3467. doi:10.1016/j.biortech.2007.08.002
  139. 139. Orvos DR, Versteeg DJ, Inauen J, Capdevielle M, Rothenstein A, Cunningham V. Aquatic toxicity of triclosan. Environ Toxicol Chem. 2002;21:1338–1349
  140. 140. Ishibashi H, Matsumura N, Hirano M, Matsuoka M, Shiratsuchi H, Ishibashi Y, et al. Effects of triclosan on the early life stages and reproduction of medaka Oryzias latipes and induction of hepatic vitellogenin. Aquat Toxicol. 2004;67:167–179. doi:10.1016/j.aquatox.2003.12.005
  141. 141. Smith GR, Burgett AA. Effects of three organic wastewater contaminants on American toad, Bufo americanus, tadpoles. Ecotoxicology. 2005;14:477–482
  142. 142. Saley A, Hess M, Miller K, Howard D, King‐Heiden TC. Cardiac toxicity of Triclosan in developing zebrafish. Zebrafish.2016; ISSN (Online) 1557–8542. doi:10.1089/zeb.2016.1257
  143. 143. Davis EF, Klosterhaus SL, Stapleton HM. Measurement of flame retardants and triclosan in municipal sewage sludge and biosolids. Environ Int. 2012;40:1–7. doi:10.1016/j.envint.2011.11.008
  144. 144. McAvoy DC, Schatowitz B, Jacob M, Hauk A, Eckhoff WS. Measurement of triclosan in wastewater treatment systems. Environ Toxicol Chem. 2002;21:1323–1329
  145. 145. Barber LB, Loyo‐Rosales JE, Rice CP, Minarik TA, Oskouie AK. Endocrine disrupting alkylphenolic chemicals and other contaminants in wastewater treatment plant effluents, urban streams, and fish in the Great Lakes and Upper Mississippi River Regions. Sci Total Environ. 2015;517:195–206. doi:10.1016/j.scitotenv.2015.02.035
  146. 146. Ivar Do Sul JA, Costa MF. The present and future of microplastic pollution in the marine environment. Environ Pollut. 2014;185:352–364. doi:10.1016/j.envpol.2013.10.036
  147. 147. UNEP, Plastic waste causes financial damage of US$13 billion to marine ecosystems each year as concern grows over microplastics. [Internet] Available from: http://www.unep.org/newscentre/ [accessed March 29, 2016]
  148. 148. Laist DW. Marine Debris. In: Coe, JM. Rogers, DB, editors. New York, NY: Springer; 1997. doi:10.1007/978‐1‐4613‐8486‐1
  149. 149. Besseling E, Wegner A, Foekema EM, van den Heuvel‐Greve MJ, Koelmans AA. Effects of microplastic on fitness and PCB bioaccumulation by the lugworm Arenicola marina (L.). Environ Sci Technol. 2013;47:593–600. doi:10.1021/es302763x
  150. 150. Wegner A, Besseling E, Foekema EM, Kamermans P, Koelmans AA. Effects of nanopolystyrene on the feeding behavior of the blue mussel (Mytilus edulis L.). Environ Toxicol Chem. 2012;31:2490–2497. doi:10.1002/etc.1984
  151. 151. Foekema EM, De Gruijter C, Mergia MT, van Franeker JA, Murk AJ, Koelmans AA. Plastic in North Sea fish. Environ Sci Technol. 2013;47:8818–8824. doi:10.1021/es400931b
  152. 152. Sussarellu R, Suquet M, Thomas Y, Lambert C, Fabioux C, Pernet MEJ, et al. Oyster reproduction is affected by exposure to polystyrene microplastics. Proc Natl Acad Sci USA. 2016;113:2430–2435. doi:10.1073/pnas.1519019113
  153. 153. Leggett W, Deblois E. Recruitment in marine fishes: is it regulated by starvation and predation in the egg and larval stages? Netherlands J Sea Res. 1994;32:119–134
  154. 154. Bailey K, Houde ED. Predation on eggs and larvae of marine fishes and the recruitment problem. Adv Mar Biol. 1989;25:1–83
  155. 155. Fossi MC, Marsili L, Baini M, Giannetti M, Coppola D, Guerranti C, et al. Fin whales and microplastics: the Mediterranean sea and the sea of Cortez scenarios. Environ Pollut. 2016;209:68–78. doi:10.1016/j.envpol.2015.11.022
  156. 156. Rochman CM, Hoh E, Hentschel BT, Kaye S. Long‐term field measurement of sorption of organic contaminants to five types of plastic pellets: implications for plastic marine debris. Environ Sci Technol. 2013;47:1646–1654. doi:10.1021/es303700s
  157. 157. Cole M, Lindeque P, Fileman E, Halsband C, Goodhead R, Moger J, et al. Microplastic ingestion by zooplankton. Environ Sci Technol. 2013;47:6646–6655. doi:10.1021/es400663f
  158. 158. Mattsson K, Ekvall MT, Hansson L‐A, Linse S, Malmendal A, Cedervall T. Altered behavior, physiology, and metabolism in fish exposed to polystyrene nanoparticles. Environ Sci Technol. 2015;49:553–561. doi:10.1021/es5053655
  159. 159. Brown DM, Wilson MR, MacNee W, Stone V, Donaldson K. Size‐dependent proinflammatory effects of ultrafine polystyrene particles: a role for surface area and oxidative stress in the enhanced activity of ultrafines. Toxicol Appl Pharmacol. 2001;175:191–199. doi:10.1006/taap.2001.9240
  160. 160. Bhattacharya P, Lin S, Turner J, Ke P. Physical adsorption of charged plastic nanoparticles affects algal photosynthesis. J Phys Chem. 2010;114:16556–16561
  161. 161. Besseling E, Wang B, Lürling M, Koelmans AA. Nanoplastic affects growth of S. obliquus and reproduction of D. magna. Environ Sci Technol. 2014;48:12336–12343. doi:10.1021/es503001d
  162. 162. Smith GS, Lumsden JH. Review of neutrophil adherence, chemotaxis, phagocytosis and killing. Vet Immunol Immunopathol. 1983;4:177–236
  163. 163. Palić D, Andreasen CB, Frank DE, Menzel BW, Roth JA. Gradient separation and cytochemical characterisation of neutrophils from kidney of fathead minnow (Pimephales promelas Rafinesque, 1820). Fish Shellfish Immunol. 2005;18:263–267. doi:10.1016/j.fsi.2004.07.003
  164. 164. Greven A‐C, Merk T, Karagöz F, Mohr K, Klapper M, Jovanović B, et al. Polycarbonate and polystyrene nanoplastic particles act as stressors to the innate immune system of fathead minnow (Pimephales promelas). Environ Toxicol Chem. 2016;9999:1–8. doi:10.1002/etc.15 3501
  165. 165. Rios LM, Moore C, Jones PR. Persistent organic pollutants carried by synthetic polymers in the ocean environment. Mar Pollut Bull. 2007;54:1230–1237. doi:10.1016/j.marpolbul.2007.03.022
  166. 166. Ogata Y, Takada H, Mizukawa K, Hirai H, Iwasa S, Endo S, et al. International Pellet Watch: global monitoring of persistent organic pollutants (POPs) in coastal waters. 1. Initial phase data on PCBs, DDTs, and HCHs. Mar Pollut Bull. 2009;58:1437–1446. doi:10.1016/j.marpolbul.2009.06.014
  167. 167. Iguchi T, Watanabe H, Katsu Y. Application of ecotoxicogenomics for studying endocrine disruption in vertebrates and invertebrates. Environ Health Perspect. 2005;114:101–105. doi:10.1289/ehp.8061
  168. 168. vom Saal FS, Hughes C. An extensive new literature concerning low‐dose effects of bisphenol A shows the need for a new risk assessment. Environ Health Perspect. 2005;113:926–933
  169. 169. Harris CA, Henttu P, Parker MG, Sumpter JP. The estrogenic activity of phthalate esters in vitro. Environ Health Perspect. 1997;105:802–811
  170. 170. Fent K, Chew G, Li J, Gomez E. Benzotriazole UV‐stabilizers and benzotriazole: antiandrogenic activity in vitro and activation of aryl hydrocarbon receptor pathway in zebrafish eleuthero‐embryos. Sci Total Environ. 2014;482:125–136. doi:10.1016/j.scitotenv.2014.02.109
  171. 171. Fry DM. Reproductive effects in birds exposed to pesticides and industrial chemicals. Environ Health Perspect. 1995;103:165–171
  172. 172. Crisp T, Clegg E, Cooper R, Wood W, Anderson D, Baetcke K, et al. Environmental endocrine disruption: an effects assessment and analysis. Environ Health Perspect. 1998;106:11–56.
  173. 173. Hirai H, Takada H, Ogata Y, Yamashita R, Mizukawa K, Saha M, et al. Organic micropollutants in marine plastics debris from the open ocean and remote and urban beaches. Mar Pollut Bull. 2011;62:1683–1692. doi:10.1016/j.marpolbul.2011.06.004
  174. 174. Holmes LA, Turner A, Thompson RC. Adsorption of trace metals to plastic resin pellets in the marine environment. Environ Pollut. 2012;160:42–48. doi:10.1016/j.envpol.2011.08.052
  175. 175. Boerger CM, Lattin GL, Moore SL, Moore CJ. Plastic ingestion by planktivorous fishes in the North Pacific Central Gyre. Mar Pollut Bull. 2010;60:2275–2278. doi:10.1016/j.marpolbul.2010.08.007
  176. 176. Davison P, Asch R. Plastic ingestion by mesopelagic fishes in the North Pacific Subtropical Gyre. Mar Ecol Prog Ser. 2011;432:173–180. doi:10.3354/meps09142
  177. 177. Rochman CM, Hoh E, Kurobe T, Teh SJ. Ingested plastic transfers hazardous chemicals to fish and induces hepatic stress. Sci Rep. 2013;3:3263. doi:10.1038/srep03263
  178. 178. Yanbin Z, Chen W, Shuang X, Jieqiong J, Rui H, Guanxiang Y, et al. Biosensor medaka for monitoring intersex caused by estrogenic chemicals. Environ Sci Technol. 2014;48:2413–2420. doi:10.1021/es4052796
  179. 179. Rochman CM, Kurobe T, Flores I, Teh SJ. Early warning signs of endocrine disruption in adult fish from the ingestion of polyethylene with and without sorbed chemical pollutants from the marine environment. Sci Total Environ. 2014;493:656–661. doi:10.1016/j.scitotenv.2014.06.051
  180. 180. Zhao Y, Hu J. Development of a molecular biomarker for detecting intersex after exposure of male medaka fish to synthetic estrogen. Environ Toxicol Chem. 2012;31:1765–1773. doi:10.1002/etc.1892
  181. 181. Moore C., Moore S., Leecaster M., Weisberg S. A comparison of plastic and plankton in the North Pacific Central Gyre. Mar Pollut Bull. 2001;42:1297–1300. doi:10.1016/S0025‐326X(01)00114‐X
  182. 182. Browne MA, Dissanayake A, Galloway TS, Lowe DM, Thompson RC. Ingested microscopic plastic translocates to the circulatory system of the mussel, Mytilus edulis (L.). Environ Sci Technol. 2008;42:5026–5031. doi:10.1021/es800249a
  183. 183. Anastasopoulou A, Mytilineou C, Smith CJ, Papadopoulou KN. Plastic debris ingested by deep‐water fish of the Ionian Sea (Eastern Mediterranean). Deep‐Sea Res Pt I. 2013;74:11–13. doi:10.1016/j.dsr.2012.12.008
  184. 184. Neves D, Sobral P, Ferreira JL, Pereira T. Ingestion of microplastics by commercial fish off the Portuguese coast. Mar Pollut Bull. 2015;101:119–126. doi:10.1016/j.marpolbul.2015.11.008
  185. 185. Romeo T, Consoli P, Castriota L, Andaloro F. An evaluation of resource partitioning between two billfish, Tetrapturus belone and Xiphias gladius, in the central Mediterranean sea. J Mar Biol Assoc United Kingdom. 2009;89:849. doi:10.1017/S0025315408002087
  186. 186. Bellas J, Martínez‐Armental J, Martínez‐Cámara A, Besada V, Martínez‐Gómez C. Ingestion of microplastics by demersal fish from the Spanish Atlantic and Mediterranean coasts. Mar Pollut Bull. 2016;S0025‐326X:30430‐30431. doi:10.1016/j.marpolbul.2016.06.026
  187. 187. Lusher AL, Mchugh M, Thompson RC. Occurrence of microplastics in the gastrointestinal tract of pelagic and demersal fish from the English Channel. Mar Pollut Bull. 2013;67:94–99. doi:10.1016/j.marpolbul.2012.11.028
  188. 188. Gregory MR. Environmental implications of plastic debris in marine settings‐‐entanglement, ingestion, smothering, hangers‐on, hitch‐hiking and alien invasions. Philos Trans R Soc Lond B Biol Sci. 2009;364:2013–2025. doi:10.1098/rstb.2008.0265
  189. 189. Farrell P, Nelson K. Trophic level transfer of microplastic: Mytilus edulis (L.) to Carcinus maenas (L.). Environ Pollut. 2013;177:1–3. doi:10.1016/j.envpol.2013.01.046
  190. 190. Setälä O, Fleming‐Lehtinen, V., Lehtiniemi M. Ingestion and transfer of microplastics in the planktonic food web. Environ Pollut. 2014;185:77–83
  191. 191. Smith BR, Blumstein DT. Fitness consequences of personality: a meta‐analysis. Behav Ecol. 2007;19:448–455. doi:10.1093/beheco/arm144
  192. 192. Lönnstedt OM, McCormick MI, Meekan MG, Ferrari MCO, Chivers DP. Learn and live: predator experience and feeding history determines prey behaviour and survival. Proc Biol Sci. 2012;279:2091–2098. doi:10.1098/rspb.2011.2516
  193. 193. Lönnstedt OM, Eklöv P. Environmentally relevant concentrations of microplastic particles influence larval fish ecology. Science. 2016;352:1213–1316. doi:10.1126/science.aad8828

Written By

Cristóbal Espinosa, M. Ángeles Esteban and Alberto Cuesta

Submitted: 09 March 2016 Reviewed: 05 July 2016 Published: 26 October 2016