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      First detection of seven phthalate esters (PAEs) as plastic tracers in superficial neustonic/planktonic samples and cetacean blubber

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          Abstract

          PAEs concentrations can serve as tracer of plastics ingestion by marine organisms.

          Abstract

          Ingestion of plastics and microplastics by marine organisms may have physical and toxicological noxious effects creating a serious threat to marine species. There is a need to develop methods to evaluate the plastic exposure in free-ranging marine wildlife particularly related to microplastic ingestion. To this aim, seven phthalate esters (PAEs) were analysed, as plastic tracers, in neustonic/planktonic samples and skin biopsy samples of four cetacean species from the North-Western Mediterranean Sea. Among all phthalates, the highest frequency of detection was obtained from DEHP (78.9%), followed in descending order by MBzP (57.9%), MEHP and BBzP (both 52.6%), DIOIP (47.4%) and MBP and DNHP (both 42.1%). All 19 superficial tows analysed presented microplastic debris, confirming the widespread distribution of microplastics on the seawater surface in the Mediterranean Sea. The abundance of the smallest items (<0.5 mm) found in the samples was significantly correlated with MEHP, MBzP and BBzP, while the abundance of 0.5–1 mm and 2.5–5 mm items were related to BBzP and MBP, respectively. Regarding the PAEs, detected in the neustonic/planktonic samples correlated with microplastics (MEHP, MBzP, BBzP and MBP), appreciable levels of these compounds were found in all the four cetacean species. The present results represent a step forward in the application of a new non-invasive analytical method to evaluate PAEs as tracers of plastic exposure/ingestion in marine wildlife.

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          Most cited references63

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          Microplastics in the marine environment.

          This review discusses the mechanisms of generation and potential impacts of microplastics in the ocean environment. Weathering degradation of plastics on the beaches results in their surface embrittlement and microcracking, yielding microparticles that are carried into water by wind or wave action. Unlike inorganic fines present in sea water, microplastics concentrate persistent organic pollutants (POPs) by partition. The relevant distribution coefficients for common POPs are several orders of magnitude in favour of the plastic medium. Consequently, the microparticles laden with high levels of POPs can be ingested by marine biota. Bioavailability and the efficiency of transfer of the ingested POPs across trophic levels are not known and the potential damage posed by these to the marine ecosystem has yet to be quantified and modelled. Given the increasing levels of plastic pollution of the oceans it is important to better understand the impact of microplastics in the ocean food web. Copyright © 2011 Elsevier Ltd. All rights reserved.
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            Accumulation and fragmentation of plastic debris in global environments.

            One of the most ubiquitous and long-lasting recent changes to the surface of our planet is the accumulation and fragmentation of plastics. Within just a few decades since mass production of plastic products commenced in the 1950s, plastic debris has accumulated in terrestrial environments, in the open ocean, on shorelines of even the most remote islands and in the deep sea. Annual clean-up operations, costing millions of pounds sterling, are now organized in many countries and on every continent. Here we document global plastics production and the accumulation of plastic waste. While plastics typically constitute approximately 10 per cent of discarded waste, they represent a much greater proportion of the debris accumulating on shorelines. Mega- and macro-plastics have accumulated in the highest densities in the Northern Hemisphere, adjacent to urban centres, in enclosed seas and at water convergences (fronts). We report lower densities on remote island shores, on the continental shelf seabed and the lowest densities (but still a documented presence) in the deep sea and Southern Ocean. The longevity of plastic is estimated to be hundreds to thousands of years, but is likely to be far longer in deep sea and non-surface polar environments. Plastic debris poses considerable threat by choking and starving wildlife, distributing non-native and potentially harmful organisms, absorbing toxic chemicals and degrading to micro-plastics that may subsequently be ingested. Well-established annual surveys on coasts and at sea have shown that trends in mega- and macro-plastic accumulation rates are no longer uniformly increasing: rather stable, increasing and decreasing trends have all been reported. The average size of plastic particles in the environment seems to be decreasing, and the abundance and global distribution of micro-plastic fragments have increased over the last few decades. However, the environmental consequences of such microscopic debris are still poorly understood.
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              Microplastics in the marine environment: a review of the methods used for identification and quantification.

              This review of 68 studies compares the methodologies used for the identification and quantification of microplastics from the marine environment. Three main sampling strategies were identified: selective, volume-reduced, and bulk sampling. Most sediment samples came from sandy beaches at the high tide line, and most seawater samples were taken at the sea surface using neuston nets. Four steps were distinguished during sample processing: density separation, filtration, sieving, and visual sorting of microplastics. Visual sorting was one of the most commonly used methods for the identification of microplastics (using type, shape, degradation stage, and color as criteria). Chemical and physical characteristics (e.g., specific density) were also used. The most reliable method to identify the chemical composition of microplastics is by infrared spectroscopy. Most studies reported that plastic fragments were polyethylene and polypropylene polymers. Units commonly used for abundance estimates are "items per m(2)" for sediment and sea surface studies and "items per m(3)" for water column studies. Mesh size of sieves and filters used during sampling or sample processing influence abundance estimates. Most studies reported two main size ranges of microplastics: (i) 500 μm-5 mm, which are retained by a 500 μm sieve/net, and (ii) 1-500 μm, or fractions thereof that are retained on filters. We recommend that future programs of monitoring continue to distinguish these size fractions, but we suggest standardized sampling procedures which allow the spatiotemporal comparison of microplastic abundance across marine environments.
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                Author and article information

                Journal
                AMNECT
                Analytical Methods
                Anal. Methods
                Royal Society of Chemistry (RSC)
                1759-9660
                1759-9679
                2017
                2017
                : 9
                : 9
                : 1512-1520
                Affiliations
                [1 ]Department of Environmental
                [2 ]Earth and Physical Sciences
                [3 ]University of Siena
                [4 ]Siena
                [5 ]Italy
                [6 ]Department of Chemistry “Ugo Schiff”
                [7 ]University of Florence
                [8 ]Firenze
                [9 ]Department of Biological and Environmental Sciences
                [10 ]University of Messina
                [11 ]Messina
                [12 ]ISPRA
                [13 ]Institute for Environmental Protection and Research
                [14 ]Roma
                Article
                10.1039/C6AY02674E
                20b6045c-4b69-4aed-9787-cef2492cbda2
                © 2017
                History

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