Marne Polation lin 6 (2011) 1506-1605 ELSEVIER journal homepage: ww Contents lists available at ScienceDirect Marine Pollution Bulletin r.com/locate/marpolbul Microplastics in the marine environment Anthony L. Andrady Department of Chem and moka Enger. North Cucina Stave Unversity, Raleigh NC 2755, USA ARTICLE INFO AmstRacT Foyer “his eve dase the mechanisms of generation apd potent npc af mieropass in the ocean Nowe Crvironment Weathering degradation of plastics on the beaches els nthe surface mite nna Sc micocacing,yiling micropatie thst are cared into water by wind or wave action. 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Introduction est plastics (Rios and Moore, 2007) with verified accounts af pe- ‘The first reports of plastics litter inthe oceans in the early 1970s (Fowler, 1987; Carpenter et al,, 1972; Carpenter and Smith, 1972; Coe and Rogers, 1996; Colton and Knapp, 1974) drew minimal attention of the scientific community. In the following decades, ‘with accumulating data on ecological consequences of such debris, the topic received increasing sustained research interest. Most studies have focused on the entanglement of marine mammals (La- ist, 1997), cetaceans (Clapham et al, 1999) and other species (Exik- son and Burton, 2003) in net fragment litter and on ‘ghost fishing” by derelict gear in the benthos (Bullimore et al, 2001: Tschernlj and Larsson, 2003). Ingestion of plastics by birds (Mallory, 2008; Cadee, 2002) and turtles (Mascarenhas et al, 2004; Bugoni and Krause, 2001; Tomas and Guitar, 2002) s extensively documented ‘worldwide and at least 44% of marine bird species are known to i. ‘malades andrady@andetycom (0025-326X/$- se fant matters 2011 Fee Al righ reserved 4101016). marptbu2011.0.020| ‘ies such as the black-footed albatross feeding plastics granules to its chicks. With recent reports on the unexpectedly high incidence ‘of plastic debris in the North Pacific gyre (Moore et al, 2001, 20012, 2002; Moore, 2008) this interest has culminated in defining the topic as a high-priority research area in Marine Biology (Der- raik, 2002; Page and McKenzie, 2004; Arthur et al, 2008). partic- ular concern is the occurrence of smaller pieces of plastic debris Including those not visible to the naked eye, referred to as micro- plastics, in the world’s aceans. This review attempts ta addvess the fate of plastics in the marine environment. the mechanisms by which microplastis are derived from marine debris and the po- tential ecological impacts of microplastics. 1.1, Plastics used in the marine environment ‘The annual global demand for plastics has consistently increased ‘over the recent years and presently stands at about 245 million‘AL Arad Marin Poltion Bulletin 62 (2011) 1506-1605 tonnes. Being a versatile, light weight, strong and potentially trans- parent material, plastics are ideally suited fora variety of applica- tons. Their low cost, excellent oxygenmoisture barrier properties, bio-inertness and light weight make them excellent packaging, ‘materials. Conventional materials such as glass, metal and paper are being replaced by cost effective plastic packaging of equivalent fr superior design. Nearly a third ofthe plastic resin production is ‘therefore converted into consumer packaging material that include disposable single-use items commonly encountered in beach debris (Andrady, 2003), How much ofthe 75-80 million tonnes of packag- ing plastics used globally each year ends up in the oceans, has not been reliably estimated. Several broad classes of plastics are used in packaging: Polyethyelene (PE), Polypropylene (PP), Polystyrene (Ps), Poly(eth- ylene terephthalate) (PET); and Poly(vinyl chloride) (PVC). Their high-volume usage is reflected in their production figures given in Table 1 and consequently these in particular have high likel hood of ending up in the ocean environment. Extensive fishing, recreational and maritime uses of the ocean, as well as changing, demographics favoring immigration to coastal regions, will in- crease the future influx of plastics waste into the oceans (Ribic et al, 2010). Land-based sources including beach litter contributes about 80% of the plastic debris. The entire global fishing fleet now uses plastic gear (Watson et a, 2006) and some gear is invariably lost or even discarded carelessly at sea during use. Polyolefins (PE and PP), as well as nylons are primarily used in fishing gear applications (Timmers et al, 2005; Klust, 1982). About 18% of the marine plastic debris found in the ocean environ- ‘ment is attributed to the fishing industry. Aquaculture can also be 4 significant contributor of plastics debris in the oceans (Hinojosa land Thiel, 2009). The rest is derived largely from land-based sources including beach litter. Virgin resin pellets, a common component of debris, enter the oceans routinely via incidental losses during ocean transport or through run-off from processing facilities (Gregory, 1996; Doyle etal, 2011; Ogata et al 2009). Quantifying floating plastic debris (generally using surface ‘water collection of debris with neuston nets) seriously underes ‘mates the amounts of plastics in the ocean as those in the sediment and mid-water are excludedby the technique. The visibility of debris a flotsam requites plastics to be positively buoyant in sea water (specific gravity of sea water is ~1.025). However, as seen from ‘Table 1 only afew of the plastis typically used in the marine em ‘ronment has aspecificgravty lower than that of seawater. (The spe- cific gravities given are forthe virgin resin: plastics in products are ‘often mixed with fillers and other additives that may alter their spe- cific gravity.) Denser varieties of plastics such as nylons tend to sub- ‘merge in the water column and even reach the coastal sediment. 1.2, Microplastics inthe oceans {A recent significant finding is that minute fragments of plastic debris, termed microplastics, occur in oceans worldwide Table lass of plastics tha are commonly encounter i the marin envionment 167 (Bares et al. 2009) including even in Antarctica (Zarfl_ and ‘Matthies, 2010). Microplastics, a form of man-made Hitter, have ‘been accumulating in the oceans for at least over the last four decades (Thompson et al., 2004, 2005). Sampled from surface ‘waters of from beach sand this fraction of litter includes virgin resin pellets, compounded masterbatch pellets and smaller Iragments of plastics derived from the larger plastic debris (Moore, 2008) ‘The term ‘microplastes’ and ‘microlitter’ has been defined differently by various researchers. Gregory and Andrady (2003) defined microliter as the barely visible particles that passthrough 2500 j1m sieve but retained by a 67 jim sieve (~0.06-0.5 mm in ameter) while particles larger than this were called mesoitter. Others (Fendall and Sewell. 2009; Betts, 2008: Moore. 2008), including a recent workshop on the topic (Arthur et al, 2008) defined the microparticles as being in the size range <5 mm (recognising 333 jim as a practical lower limit when neuston nets are used for sampling Particles of plasties that have dimensions ranging from a few jim to 500 jum (5 mm) are commonly present in sea water (Ng and Obbard, 2006; Bares et al, 2009). For clarity, this size range alone is referred to as microplastics'here; the larger particles such as virgin resin pellets are referred to as ‘mesoplas- tics’ after Gregory and Andrady (2003). Persistent organic pollutants (POPs) that occur universally in sea water at very low concentrations are picked up by meso-|microplastcs via partition- ing Is the hydvophobicity of POPs that facilitate their concentra tion in the meso-|microplastc liter at a level that is several orders fof magnitude higher than that in sea water. These contaminated plastics when ingested by matine species presents a credible route bby which the POPS can enter the marine food web. The extent of bioavailability of POPs dissolved in the microplastics to the biota (Moore, 2008) and their potential bio-magnification in the food ‘web (Teuten et al, 2007) has not been studied in detail. Unlike larger fragments microplastics are not readily visible to the naked eye: even resin-pellets (mesoplastics) mixed with sand are not easly discernible. Net sampling does not of course collect the smaller microplastics and no acceptable standard procedure is presently available for their enumeration in water or sand. The following is only 2 suggested procedure derived from published reports as well as personal experience of the author. Water samples ae filtered through a coarse filter to remove ‘mesolitter. Sediment or sand samples are sluried in saline water to allow microplastics to float to the surface. A mineral salt may be dissolved in the collected sea water or slurry sample to increase the water density suficiently to float plastic fragments. Samples of surface water with floating microparticles are carefully removed {or study. Concentrating samples of sea water samples by evapora- tion can also concentrate the microplastic litter at the surface ‘Microplastics in surface water samples can be visualised under a microscope using a lipophilic dye (such as Nile Red) to stain them (Andrady, 2010). The water samples will also contain microbiota such as plankton of the same size range but these will not be Specific Cavity_Peventae production” Products apd Wpical ori Pasi Gass Taw-easiy pbetylene UDPELIDPE Og1-093 21m High-density poyetylene HOPE 08 vs Potpropyene ” 085-089 2a Polystyrene s 105 rs Fooed Polystyrene Nylon ma ax Thermoplastic Polyester PEE 1 m Pobvinl chloride) PVC 138 198 Coloe estate o Paste Bags sk pack ings, Bos, land juice gs Rope, bate caps neti Paste uteri ood containers Fats ai boxes, fom ce Neting and raps Paste beverage bles Paste ir, btles cups gare ters i dening Saws "ation ofthe lal pasties production a 2007 afer (Une, 2007)stained by lipophilic dyes. Digestion of the sample with hot dilute ‘mineral acid can be used to remove the biomass impurities as the treatment will not have any impact on the microplasties fraction. Microplastics suspensions might be identified using. optical ‘microscopy, electron microscopy, Raman spectroscopy and FTIR spectroscopy. The Fig. | below shows a schematic ofthis suggested sampling approach designed to isolate microplastics. As a prelude to discussing the mechanisms responsible for generation of microplastics, understanding the light-induced degradation and biodegradation of plastics in the marine ‘environment is important. 1.3. Plastics degradation under marine conditions Degradation is a chemical change that drastically reduces the average molecular weight of the polymer, Since the mechanical integrity of plastics invariably depends on their high average ‘molecular-weight, any significant extent of degradation inevitably ‘weakens the material. Extensively degraded plastics become brittle ‘enough to fall apart into powdery fragments on handling. Even these fragments, often not visible to the naked eye, can undergo ‘AL Andrady Marine Potion Balen 62 (2011) 1596-1605 further degradation (generally via microbial-mediated biodegrada- tion) with the carbon in polymer being converted into COz {and incorporated into marine biomass). When this process goes ‘onto completion and all the organic carbon in the polymer is ‘converted, it is referred to as complete mineralisation (Andrady, 1994, 1998; Eubeler et al, 2009). Degradation is generally classified according to the agency ‘causing it. (a) Biodegradation - action of living organisms usually microbes. (b) Photodegradation ~ action of light (usually suntight in ‘outdoor exposure). (©) Thermooxidative degradation ~ slow oxidative breakdown at moderate temperatures. (a) Thermal degradation’ ~ action of high temperatures {@) Hydrolysis - reaction with water. “Not an environmental degradation mechanism. ‘With common polymers such as LDPE, HDPE, PP and nylons ‘exposed to the marine environment it is primarily the UV-B Surry of Beach Sand in Sea Water | Coarse Filtration to Remove Macroliter I <> (a Spectroscopy and imaging, Fluorescent Techniques ‘Microspectroscopy <2 Mleropasis cron micoxoy SIE Sea Water Surry of Beach Sand in Sea Water a ™ Filtrate with microparticles Salt addition and Float/Filter Filtrate Concentrated and imaged - Fig. 1. Proposed scheme fr lation of pastes rm samples of water o sad 100 Eos | fsa 2 | g . 2 2 ® | AIR. 00 25 50 75 10 125 150 Duration of Exposure (months) Fig2. (Let): change in pre ‘shone panies to sce water environment (Mami Beach, FU) orignal tense extensibility of polypropylene tape exposed in aan Noting nse waterin Bayne yg) The Mtg ig sed 10‘AL Arad Marine Poltion Bulletin 62 (2011) 1506-1605 1599 sadiation in sunlight that initiates photo-oxidative degradation. (Once initiated, the degradation can also proceed thermooxidatively {ior some time without the need for further exposure to UV radia- tion. The autocatalytic degradation reaction sequence can progress as long as oxygen is available to the system. On degradation the ‘molecular weight of the polymer is decreased and oxygen-rich functional groups are generated in the polymer. Other types of degradation processes are orders of magnitude slower compared to light-induced oxidation. Hydrolysis is usually not a significant ‘mechanism in seawater. While all biomaterials, including plastics, will invariably biodegrade in the marine environment, the rate of this process, even in the benthic sediment, is several orders of ‘magnitude slower compared to light-induced oxidative degrada- tion of plastics. Degradation initiated by solar UV radiation is a very efficient mechanism in plastics exposed in ait ot lying on a beach surface But when the same plastic material is exposed to sunlight at the same location but while floating in seawater, degradation is severely retarded. Andrady and Pegram (1990, 1989a,b) and Andrady et al. (1993) compared the loss of mechanical integrity of several common packaging and gear-related plastics exposed while floating in sea water with these exposed in air at the same sites (in Biscayne Bay, FL and Pugeot Sound, WA) The dramatic reduction in the degradation rate obtained is illustrated in Fig. 2 (left) with the data for polypropylene tape. Tensile extensibility (C8) was used as the measure of degradation in the study and near-embrittlement was the end-point of interest as degradation to this extent precluded entanglement of marine mammals on the debris. Other varieties of plastics exposed on beach or in water also unslergo similar degradation, For instance, the degradation of fishing gear by sunlight has been studied by Al-Oufi et al. (2004) and Meenakumari and Radhalakshmi (1995, 1988). The weather- ing of specific gear-related plastics such as polyethylene netting, (Meenakumari and Ravindran, 1985ab), nylon monofilament ‘exposed in air at marine sites (Meenakumari and Radhalakshmi, 1988; Thomas and Hridayanathana, 2006) and twine Meenakumari and Ravindran, 1985), 1988) has been reported ‘The retardation of degradation in plastics exposed to the cle- ‘ments while floating in sea water is primarily the result of the rel- atively lower temperatures and the lower oxygen concentration in ‘ater environments. Unlike samples exposed in ait, the sample Temperatures are maintained at the lower water temperature, retarding the reaction. The discrepancy in the degradation rates (between air and floating exposures) is further exacerbated by fouling effects. Floating plastics will readily develop extensive sur- face fouling, rapidly covering the debris surface frst with a biofilm followed by an algal mat and then a colony of invertebrates (Muth- ‘ukumar etal, 2071), Initial rate of biofouling depends on the sur- face energy S ofthe plastic: materials with S between 5 and 25 mNj ‘mare minimally fouled (Kerr and Cowling, 2003). The succession of epibionts that develop on the surface colony was reported for exposures in Biscayne Bay, FL (Andrady and Song, 1991); the sequence was bacteria ~ diatoms -» hydroids -» ectocar- pales — bamacles -- bryozoans. The sequence as well as the kinetics of fouling, however, strongly depend on water conditions as well asthe season of expasute. The plastic debris gets encrusted ‘with foulants, increasing in density as fouling progresses. Once the density exceeds that of sea water it can sink well below the water surface (Costerton and Cheng, 1987; Andrady and Song, 1991; Railkin, 2003), Subsequent cle-fouling in the water column due to Toraging of foulants by other organisms oF other mechanisms, can decrease its density causing the debris to return back to the surface. A slow cyclic ‘bobbing’ motion of floating plastic debris attributed to this eyclic change in density on submersion below a Certain depth of water, was proposed by Andrady and Song (1991) and later confirmed (Stevens and Gregory, 1996; Stevens, 1992), Fouled debris may increase in density enough to ultimately reach benthic regions; plastics do occur commonly in the benthos (Stefatos and Charalampakis, 1999; Katsanevakis et al, 2 Backhurst and Cole, 2000), Even an extensively weathered, embrittled plastic material, (that falls apart on handling) still has an average molecular weight inthe tens of thousands gjmol The logarithmic plot of the tensile extensibility (%) versus the number-average molecular weight for LDPE that had undergone weathering shown in Fig, 3 illustrates this. Even for the data points at the very left of the plot (corre- sponding to extensively degraded or embritted plastic) the values ‘of M;~ 10°-10* gimol. Even at these lower molecular weights plastics do not undergo ready biodegradation. Ready microbial biodegradability has been observed in oligomers of about 'M, ~ 500 gimol polyethylenes. Reduction in particle size by light-induced oxidation does is no guarantee of subsequent biodegradability of the meso- or microplastic fragments, High molecular weight plastics used in common applications do not biodegrade at an appreciable rate as microbial species that can ‘metabololize polymers are rate in nature. This is particularly true of the marine environment, with the exception of biopolymers such as cellulose and chitin. Recent work, however, has identified several strains of microbes capable of biodegrading polyethylene (Sivan, 2011) and PVC (Shah et al, 2008). In concentrated liquid culture in the laboratory, Actinomycetes Ritodococcus ruber (strain (€208) resulted in a reduction of ca. 8% in the dry weight of the polyolefin within 30 days of incubation (Cilan et al., 2004). Lac- cases secreted by the species reduced the average molecular ‘weight of polymer as demonstrated by GPC indicating degradation via scission of main chains. However, this process does not occur in soil oF marine environments as the candidate microbes are not available in high enough native concentration and competing casily-assimilable nutrient sources are always present, ‘There is virtually no data on Kinetics of mineralisation of plastics in the marine environment. However, biopolymers such as chitins (Poulicek and Jeuniaux, 1991; Seki and Taga, 1963), hitosan (Andrady et al, 1992), and a few synthetic polymers such as aliphatic polyesters do biodegrade rapidly at sea (Mayer and Kaplan, 1996; Doi et al, 1992: Leathers et al. 2004), Starch-flled polyolefins (Gonsalves and Patel, 2003; Breslin and Boen, 1993) are sometimes erroneously referred to as ‘biodegradable’, but only the starch fraction undergoes ready mineralisation in the marine environment, Ideally, the polymer material disposed in the environment should biodegrade completely releasing the carbon into the carbon cycle. Mineralisation is the complete conversion ‘of carbon that constitutes the plastics into CO,, water and biomass. 000 Foo | _serehaterl eel 8 Anarady ea 20 ——— 2 __ 1 1 10 100 Percentage of Original Tensile Extensibility Fig 3. Two sets of data showing the relationship between uber average ‘molecule eight Ana the perentFelention of extesity of depraded ple ‘lene The pper sts or dat for high-density poletlene ods in oxygen C100 ¢ (Remco and Home 1984), Upper sti or poyethyeneb) 3d CONG + (22485 2 200; *41L04dNHs for Gd>b) “The rate of carbon conversion under simulated marine exposure is measured in the laboratory using respirometry (Eubeler et a, 2008; Sha et al, 2008; Allen and Mayer, 1994). Finely-divided polymerisincubated ina boticmedium suchas coastal marine sed {ment and the catbon dioxide gas evolved during biodegradation is ‘quantified. To accelerate mineralisation, the medium is typically enriched with urea (N)/ Phosphates (P). and seeded with an active microbial culture. The carbon dioxide is estimated ttrimetrcally ‘and the percent conversion of carbon from polymer to gas-phase is calculated. This forms the basis ofthe Sturm test widely used with ‘organic compounds. Assessment of Biodegradation of polymers was reviewed (Andrady, 1994; Eubeler et al, 2008: Shah eta. 2008) Even under optimum laboratory conditions, in soi seded with activated sewage sludge consotia, the rate of CO, evolution from biodegradation of polyolefins i so slow that “C-labelled polymer was used to monitor the process (Albertson, 1978: Albetsson ‘and Karlsson, 1988), Recent data show <1.2% carbon conversion ‘vera 3-month period (Abrusc et a, 2011) inagreement with pre- vious rate determinations. Pre-oxiised (extensively degraded) polymers will biodegrade ata faster rate. Rates of 02% and 5.7% ‘atbon conversion per 10years for low-density. polyethylene [LDPE] without and with pre-photodegradation were reported, respectively. Guillet et al reported biodegradation of pre-photoox- idized polystyrene in soil with growing plants to proceed ata rate ‘of ~5% over 6 months (Guile et al, 1988). However, these results are likely to be overestimates as the lower molecular-weight poly- imer fraction and hydrophilic oxygenated degradation products from extensive pre-degradation (Andrady and Pegram, 1993) are likely to initially biodegrade rapidly. In any event the finding is oflittle practical consequence. Embrittlement in beach weathering increases the specific surface area ofthe plastics by several orders ‘of magnitude and this might be expected to increase its rate of bio- ‘degradation (Kawai ea, 2004). Bu, this small increase inthe rate ‘of am already very slow process to effect its complete mineralisa- tion ina reasonable timescale of a few yeas. The laboratory results ‘are generally consistent with the findings from field exposures HDPE, LDPE and PP coupons immersed in Bay of Bengal (India) ‘observed over a 6-month periods in a recent study. Maximum ‘weight loss was in LDPE (1.5-2.5%), followed by that in HDPE (05-08%) and PP (0.5-0.6%) (Sudhakar and Doble, 2008). 1.4. Origins of microplatics How are microplastis in the oceans generated? The origins of the microplastics might be attributed to two main sources: (a) direct introduction with runoff and (b) weathering breakdown of ‘meso- and macroplastics debris. Some microplastics, especially the manufactured micro- and nanoparticles of plastics used in ‘consumer products (Maynard, 2006), are introduced directly into the oceans via runoff. These include the micron-sized plastic pati- ‘les are typically used as exfoliants in cosmetic formulations (Gregory, 1996; Fendall and Sowell, 2009), those generated in ship-breaking industry (Reddy and Shaik, 2006) and industrial abrasives in synthetic ‘sandblasting’ media (beads of acrylic plas- tics and polyester). These can easily reach the oceans via runoff. ‘The likely mechanism for generation of a majority of microplas- ties, however, isthe in situ weathering of mesoplastics and larger fragments of plastic liter in the beach environment (Gregory and ‘Andrady, 2003). Plastic litter occurs on beaches, surface water ‘and deep water environments but as already pointed out the rates ‘of weathering in these three sites will be very different. Unlike those floating in water, plastics litter lying on beaches is subjected to very high temperatures. Given the relatively low specific heat of sand (664 J/kg-C), sandy beach surfaces and the plastic litter on it ‘can heat up to temperatures of ~40 °C in Summer. Where the plas- tic debris is pigmented dark, the heat build-up due to solar infra- red absorption can raise its temperature even higher (Shaw and Day, 1994):The light-initiated oxidative degradation is accelerated at higher temperatures by a factor depending on the activation ‘energy E, of the process. Where the E, ~'50 kjimole for instance, the rate of degradation doubles when the temperature rises by only 10°C. Especially with opaque plastics, nearly all the initial oxidative breakdown occurs at the surface layers. This localised degradation isbecause ofthe high extinction coefficient of UV-B radiation in plas- tics, the diffusion-controlled nature of oxidation reaction (Cunliffe and Davis, 1982) and the presence of fillers that impede ‘oxygen diffusion in the material Degradation occurs faster in ‘virgin pellets that contain no UV stabilizers compared to that inplas- ties produets, Net result of this made of oxidative degradation is a weak, brittle surface layer that develops numerous microcracks and pits as shown in the micrographs in Fig. 4 (Qayyum and White, 1993; Blaga and Yamasaki, 1976; Blaga, 1980). This degraded fragile surface is susceptible to fracture by stress induced by humidity or temperature changes as well abrasion against sand (George, 1995). “Microparticles of plastics are derived from this brittle surface layer. Surface microcracking is commonly observed in UV-exposed plas- tics including HDPE (Akay et al, 1980), LDPE (Kupper et al, 2004; Tavares et al, 2003), polycarbonate (Blaga and Yamasaki, 1975) and polypropylene (Qayyum and White, 1993; Yakimets et al, ! \ Fig. Rig: P exposed oa 600 wat xenon sure for Breck (Yai ts, 200); Mille: PP expose fort week under desert exposure cndions (Qayyum and Whit 1952}: Lets LDPE weathered in weaheromete or 8008 (Kapp, ts, 2004)‘AL Arad Marine Poltion Bulletin 62 (2011) 1596-1605 1601 2004). Consistent with these findings, extensive microcracking and pitting is reported on mesoplastic debris collected from beaches as well (Cooper and Corcoran, 2010; Gregory, 1983; Ogata et al, 2009). Polypropylene rope sample that had weathered on a pier {or several years (provided courtesy of Capt. Charles Moore, Algalita Marine Foundation) when extracted with distled water yielded Jarge amounts of plastic microplastics that were visualised by stain- ing with Nile Red (Andrady, 2010) “The same degradation does not occur in plastics exposed while floating in water. As pointed out already, the low water temperature and foulant effects retard the process dramatically. Plastics that are directly discarded into the water (from vessels) or litter washed into the water prior to any significant weathering degradation are also unlikely to yield microplastics via this mechanism. The same is true of plastics debris that sink in the water column, The lack of UV-B (rapidly attenuated in ea water)to initiate the process, the low tem- peratures and the lower oxygen concentration relative to that ina, ‘makes extensive degradation fa less likely than forthe floating plas- tics debris. Thus the most likely site for generation of microplastics in the marine environment is the beach. Recognition that microparticles (and! therefore also nanoplas- tics) are most likely generated on beaches underlines the impor- tance of beach cleaning as an effective mitigation strategy. The removal of larger pieces of plastic debris from beaches before these are weathered enough to be surface embritted can have consider- able value in reducing the microplastics that end up in the ocean. Beach cleanup therefore can have an ecological benefit far beyond the aesthetic improvements ofthe beaches, and by reducing micro- plastics, contributes towards the health of the marine food web. 1.5. Toxicity of ingested microplasties ‘Sea water already contains numerous natural micro- and nano- particles (~10°-10” particles per mil or 10-500 jig) most of them 100 nm in size (Rosse and Loizeau, 2003) Filter feeders in the ‘ocean ranging from the nano-zooplanktons to Balleen Whales, rou- tinely interact with these without any apparent ill effect. As no enzymatic pathways available to break down the synthetic poly- ‘mers in any of these organisms, ingested of microplastics are also never digested or absorbed and should therefore be bio-inert Ingestion of microplastis by microbiota, however, presents a very different problem. The concern is theit potential for delivery of concentrated POPS, mainly those picked up from sea water, 10 the organisms (Bowmer and Kershaw, 2010). It is this dissolved POPS that yield the toxie outcomes. Any toxicity associated with plastics in general, including meso ‘or microplastcs, can he attributed to ane or more ofthe following, factors: (a) Residual monomers from manufacture present in the plastic ‘or toxic additives used in compounding of plastic may leach ‘out of the ingested plastic. (An example of residual mono- ‘mer i illustrated by the recent issue on residual bis-phenol ‘A (BPA) in polycarbonates products (Vandenberg et al. 2007), The potential toxicity of phthalate plasticizers used in PVC has been widely discussed in the literature (Latini et al, 2004),) (b) Toxicity of some intermediates from partial degradation of plastics. Fr instance, burning polystyrene can yield styrene ‘and other aromatics and a partially burnt plastic may con- {ain significant levels of styeene and other aromatics. (c) The POPs present in sea water are slowly absorbed and con- ‘centrated in the microplastic fragments. Plastics debris does ‘lean’ the sea water ofthe dissolved pollutant chemicals. On being ingested, however, these can become bioavailable to the organisms (Endo et al, 2005) ‘The risk posed by the high concentrations of POPS picked up from the sea water is particularly significant. Sea water typically contains low levels of a host of ehemical species such as insect cides, pesticides and industrial chemicals that enter the ocean via waste water and runoff (Wurl and Obbard, 2004) POPs such as polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs), and perfluorooctanoic acid (PFOA) have a very large water-polymer distribution coefficient, Kw [Lk], in favour of the plastic. A linear isotherm model relates the mass of the chem- ‘cal sorbed per unit mass of solid polymer (q.)[1is/kg] to the equi librium solute concentration (C.) [git] by the following equation: Ge = Kw Ce a ‘where Ky (L)kg) is the equilibrium distribution coefficient for the system, This coefficient js approximated sometimes by the lipid water distribution coefficient. However, this may underestimate the polymer-water distribution coefficient seriously for some POPS (Friedman et at, 2009), The distribution of organic micropollutants in hydrophobic plastics has been studied in polypropylene pellets (Rice and Gold, 1984) and polyethylene strips (tested as potential passive sam- pling devices) (Fernandez et al, 2009; Mller et al, 2001; Adams et al, 2007), Karapanagioti and Kiontza (2008) estimated the dis- tribution coefficient Kpyy for phenanthrene, a model POP. in virgin plastic/sea water system; values of Ky (L/kg) of 13,000 for PE and 380 for PP was reported, A second study by Teuten etal, 2007 re- ported the uptake of phenanthrene by three types of plastics, con. luding the distribution coefficients to be ranked as follows: Polyethylene = Polypropylene > PVC. Values of Kew [L)kg] of ~10" {or polyethylene and ~10° for polypropylene were reported. Importantly, they established that desorption of the contaminant (back into water) was a very slow process and that even the sedi ‘ment tended to desotb the phenanthrene faster than plastics frag- ‘ments. Others reported similar high values for Keyw (L/kg] in ‘common polymers; these include Lohmann et al. (2005) who re- ported 27,000 kg for polyethylene, and Mato etal. (2001) who re- ported even higher values for PCBs in polypropylene. The reported high variability ofthe experimental Kypw values in literature can be attributed to differences in water temperature, the degree of erys- tallinty of the plastic and non-equilibrium effects. These values imply that plastic meso- and microparticles in the ocean will at equilibrium yield a highly concentrated source of POPS. ‘A recent study by Rios and Moore (2007) on plastic mesoopar- ticles on four Hawaiian, one Mexican and five California beaches showed very significant levels of pollutants in the particles. The ranges of values reported were: 5° PAH=39-1200ngig: > PCB = 27-980 ng/g: $= DDT = 22-7100 agi. These are cumulative values for 13 PCB congeners and 15 PAHls.The cumulative levels {ound in plastic pellets collected from locations near industrial sites were understandably much higher. Highest values reported ‘were > PAH = 12,000 ngig and DDT=7100 ng/g. A 2008 study re- ported data for 8 US beaches (of which 6 were in CA) as follows (Ogata et al, 2009): S> PCB = 32-605 ng/g: 5: DDT =2-106 ngig: and 5> HCH(4 isomers) = 0-0.94 ngig, The levels of pollutants in plastic pellets floating in surface layers are comparable to the range observed for sediment concentration of the same com- pounds. Recent work has suggested that micro- and mesoplastic debris may also concentrate metals (Ashton et al, 2010) in addi- tion to the POPS. This is an unexpected finding as the plastics are hydrophobic but the oxidised surface could catry functionalities that can bind metals. “The situation is reversed in the case of residual monomer and additives compounded into plastics as well as partially degraded plastics carrying degradation products. These plastics debris will slowly leach out a smal fraction of the POPS (additives, monomer