Methodology Used for the Detection and Identification of Microplastics—A Critical Appraisal
Abstract Microplastics in aquatic ecosystems and especially in the marine environment represent a pollution of increasing scientifi and societal concern, thus, recently a substantial number of studies on microplastics were published. Although fi steps towards a standardization of methodologies used for the detection and identifi
of microplastics in environmental samples are made, the comparability of data on microplastics is currently hampered by a huge variety of different methodologies, which result in the generation of data of extremely different quality and resolution. This chapter reviews the methodology presently used for assessing the concentration of microplastics in the marine environment with a focus on the most convenient techniques and approaches. After an overview of non-selective sampling approaches, sample processing and treatment in the laboratory, the reader is introduced to the currently applied techniques for the identifi and quantifi of microplastics. The subsequent case study on microplastics in sediment samples from the North Sea measured with focal plane array (FPA)-based micro-Fourier transform infrared (micro-FTIR) spectroscopy shows that only 1.4 % of the particles visually resembling microplastics were of synthetic polymer origin. This fi emphasizes the importance of verifying the synthetic polymer origin of potential microplastics. Thus, a burning issue concerning current microplastic research is the generation of standards that allow for the assessment of reliable data on concentrations of microscopic plastic particles and the involved polymers with analytical laboratory techniques such as micro-FTIR or micro-Raman spectroscopy.
Keywords Detection of microplastics • Focal plane array-based micro-FTIR imaging • Identifi of microplastics • Microplastic • Microplastic analysis • Micro-FTIR spectroscopy
Since the middle of the 20th century, the increasing global production of plastics is accompanied by an accumulation of plastic litter in the marine environment (Barnes et al. 2009; Thompson et al. 2004). Being dispersed by currents and winds, persistent plastics, whether deliberately dumped or accidentally lost, are rarely degraded but become fragmented over time (Thompson 2015). Together with micro-sized primary plastic litter from consumer products, these degraded secondary micro-fragments lead to an increasing amount of small plastic particles, so called “microplastics” (i.e. particles <5 mm) in the oceans (Andrady 2011). Microplastics are further divided according to their size into “large microplastics” (1–5 mm) and “small microplastics” (20 µm–1 mm) (Hanke et al. 2013).
The distribution of microplastics in the marine environment is strongly dependent on their density. The density of a virgin-polymer particle is often altered during the manufacturing process (e.g. density increase due to addition of inorganic fillers, density decrease due to foaming of the polymer) as well as through ageing or biofouling processes (Harrison et al. 2011; Morét-Ferguson et al. 2010; Gregory 1983). Since most synthetic polymers have a lower density than seawater, microplastic particles mostly float at the sea surface (0.022–8,654 items m−3) but occur to a lower extent suspended in the water column (0.014–12.51 items m−3). Sediments seem to represent a sink for microplastics (18,000–125,000 items m−3 in subtidal sediments) while beaches, as intermediate environments, can accumulate floating, neutrally buoyant as well as sinking plastics (185–80,000 items m−3) (Hidalgo-Ruz et al. 2012).
The massive accumulation of microplastics in the oceans has been recognized by scientists and authorities worldwide, and previous studies have demonstrated the ubiquitous presence of microplastics in the marine environment (Browne et al. 2010; Hidalgo-Ruz and Thiel 2013; Ng and Obbard 2006; Claessens et al. 2011; Van Cauwenberghe et al. 2013; Vianello et al. 2013). Thus, with the Marine Strategy Framework Directive (MSFD-indicator 10.1.3) the EU prescribes a mandatory monitoring of microplastics (Zarfl et al. 2011), and the EU Technical Subgroup on Marine Litter (TSG-ML) proposed a standardized monitoring strategy for microplastics in the EU (Hanke et al. 2013).
Researchers worldwide report on the uptake of microplastics by various marine organisms (Cole et al. 2013; Ugolini et al. 2013; Foekema et al. 2013; Murray and Cowie 2011; Browne et al. 2008). Ingestion of microplastics may lead to “… potentially fatal injuries such as blockages throughout the digestive system or abrasions from sharp objects…” (Wright et al. 2013), which, in contrast to macroplastics, mainly affect microorganisms, smaller invertebrates or larvae. In addition to these physical effects on single organisms, the ecological implications can be even more severe as microplastics can release toxic additives upon degradation and accumulate persistent organic pollutants (POPs) (Bakir et al. 2012; Engler 2012; Rios et al. 2007; Teuten et al. 2009; Rochman et al. 2013). Because of their minute size, microplastics harbor the risk of entering marine food webs at low
trophic levels and propagating toxic substances up the food web (Besseling et al. 2013; Mato et al. 2001). However, this is discussed controversially in the literature and several studies suggest that this issue is of minor importance from a risk assessment perspective (compare, e.g. Gouin et al. 2011; Koelmans et al. 2013, Koelmans 2015). Nevertheless, microplastics harbor the risk of transporting POPs to human food (Engler 2012). Because of their long residence time at sea plastics can travel long distances (Ebbesmeyer and Ingraham 1994) and thus function as vectors for dispersal of toxins and/or pathogenic microorganisms (Harrison et al. 2011; Zettler et al. 2013). However, although the potential risks associated with marine microplastics have recently been acknowledged the manifold impacts of microplastics on the ecosystems of the oceans have not been investigated in detail and are thus only poorly understood.
Current microplastic research suffers from insufficient reliable data on concentrations of microplastics in the marine environment and on the composition of involved polymers because standard operation protocols (SOP) for microplastic sampling and detection are not available (Hidalgo-Ruz et al. 2012; Claessens et al. 2013; Imhof et al. 2012; Nuelle et al. 2014). Although first steps towards a standardization have been made, e.g. in the European Union by TSG-ML (Hanke et al. 2013), the comparability of data on microplastics is still hampered by a huge variety of different methods that lead to the generation of data of extremely different quality and resolution.
In this chapter, we will critically review the methodology presently used for assessing the concentration of microplastics in the marine environment. We will focus on the most convenient techniques and approaches recently applied for the identification of microplastics. After an overview of non-selective sampling approaches and sample processing in the laboratory, we will introduce the reader to currently applied detection techniques for microplastics. Finally, we present a case study to emphasize the importance of verifying the synthetic polymer origin of potential microplastics by e.g. micro-Fourier transform infrared (micro-FTIR) spectroscopy. In an outlook, we will address important gaps in knowledge concerning the detection of microplastics and how these could be potentially filled.