Environmental Pollution 184 (2014) 161e169

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Environmental Pollution
journal homepage: www.elsevier.com/locate/envpol

A new analytical approach for monitoring microplastics in marine

sediments
Marie-Theres Nuelle a, b, Jens H. Dekiff a, b, Dominique Remy b, Elke Fries a, *,1
a
Institute of Environmental Systems Research, University of Osnabrueck, Barbarastraße 12, D-49076 Osnabrueck, Germany
b
Department of Biology/Chemistry, Division of Ecology, University of Osnabrueck, Barbarastraße 13, D-49076 Osnabrueck, Germany

a r t i c l e i n f o a b s t r a c t

Article history: A two-step method was developed to extract microplastics from sediments. First, 1 kg sediments was
Received 11 November 2012 pre-extracted using the air-induced overflow (AIO) method, based on fluidisation in a sodium chloride
Received in revised form (NaCl) solution. The original sediment mass was reduced by up to 80%. As a consequence, it was possible
15 July 2013
to reduce the volume of sodium iodide (NaI) solution used for the subsequent flotation step. Recoveries
Accepted 20 July 2013
of the whole procedure for polyethylene, polypropylene (PP), polyvinyl chloride (PVC), polyethylene
terephthalate (PET), polystyrene and polyurethane with sizes of approximately 1 mm were between 91
Keywords:
and 99%. After being stored for one week in a 35% H2O2 solution, 92% of selected biogenic material had
Density separation
Marine plastic debris
dissolved completely or had lost its colour, whereas the tested polymers were resistant. Microplastics
North Sea were extracted from three sediment samples collected from the North Sea island Norderney. Using
Pyrolysis pyrolysis gas chromatography/mass spectrometry, these microplastics were identified as PP, PVC and PET.
Gas chromatography Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction marine and coastal environment and human activities all over the
world” (UNEP, 2009). For example, in the German Bight (North Sea)
Following the invention of the first modern plastic “Bakelit” in anthropogenic debris was one of the three major flotsam categories
1907, inexpensive high-volume manufacturing techniques were (32.4 items/km2); more than 70% of floating debris was made up of
developed. These resulted in the rapidly growing mass production plastic items (Thiel et al., 2011). It is assumed that microplastics that
of plastics, which for the most common polymer types commenced are no longer visible to the naked eye represent a major element of
in the 1930s and 1940s (Cole et al., 2011). Today, we cannot imagine the global problem (Cole et al., 2011; Andrady, 2011).
life without plastics, which are used in a vast array of fields for use As an amendment to the Marine Strategy Framework Directive
in packaging, construction, medicine, electronics, automotive and (European Parliament and the Council, 2008) the “composition of
aeroplane components (Goodship, 2007). In 2009, 230 million tons micro-particles (in particular microplastics) has to be characterised
of plastics were produced globally per year. Europe is the second in marine litter in the marine and coastal environment” (European
major region of plastic production (Plastics Europe, 2010). Germany Parliament and the Council, 2010). However, there is still little
is the third major plastic producer after China and the USA (Abts, monitoring data on the occurrence of microplastics in sediments,
2010). According to sea-based sources such as shipping, fishing since analytical methods have yet to be developed. Several at-
and transport activities (Horsman, 1982; Pruter, 1987; Derraik, tempts have been made to monitor microplastics in sediments
2002) and land-based sources such as tourism, adjacent in- based on density separation in solutions of sodium chloride (NaCl)
dustries or river inputs (e.g. Reddy et al., 2006; Browne et al., 2010), (Thompson et al., 2004; Reddy et al., 2006; Browne et al., 2010;
plastics are entering our seas and oceans, “posing a complex and Claessens et al., 2011). Higher density salts such as zinc chloride
multi-dimensional challenge with significant implications for the (Imhof et al., 2012; Liebezeit and Dubaish, 2012) and polytungstate
(Corcoran et al., 2009) were used to enable to higher density
polymers to be extracted. One important issue in the extraction of
microplastics from sediments is the sediment sample mass applied
* Corresponding author. for extraction. When NaCl was used for density separation, 1 kg
E-mail address: [email protected] (E. Fries).
1
Present address: Direction Eau, Environnement et Ecotechnologies, Bureau de
sediments was usually extracted (Thompson et al., 2004; Reddy
Recherches Géologiques et Minières (BRGM), 3, Avenue Claude Guillemin, B.P. et al., 2006; Claessens et al., 2011), with the exception of Browne
36009, 45060 Orléans Cedex 02, France. et al. (2010), who used a sediment volume of only 50 mL. When

0269-7491/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.envpol.2013.07.027
162 M.-T. Nuelle et al. / Environmental Pollution 184 (2014) 161e169

expensive higher density salts were used, the sample volume was
as low as 500 mL (Liebezeit and Dubaish, 2012) and 68 mL (Imhof
et al., 2012). Corcoran et al. (2009) used a sample mass between 150
and 190 g. The reason for using such low sample volumes could be
to cut analytical costs by decreasing the amount of high-density
salts, which are expensive. However, since the distribution of
microplastics in sediments could be very low or heterogeneous in
some areas, it is advantageous to have a large sample quantity.
Increasing the sample volume increases the prospects of detecting
microplastics, and also guarantees that random samples are
representative of the study areas.
Another challenge involved in analysing microplastics in sedi-
ments is the presence of biogenic organic matter. It often has a low
density, meaning that it floats on the surface of the salt solution and
adheres to the filter. Shaw and Day (1994) reported difficulties in
optically distinguishing plastics from other organic matter when
analysing microplastics. For this reason, Liebezeit and Dubaish
(2012) suggested pretreating sediments using a solution of 30%
H2O2 to remove natural organic debris.
The aim of the present study was to develop an extraction
technique for separating microplastics from sediments. The tech-
nique consists of the following two steps: (i) fluidisation of sedi-
ments in a saturated NaCl solution and (ii) a subsequent flotation of
microplastics in a high-density salt solution. Since we wish to work
with environmentally friendly chemicals and to ensure maximum Fig. 1. Plastic particles used for recovery experiments.
cost-effectiveness, sodium iodide (NaI) was selected for the second
step. The distribution of microplastics in sediments is often het-
erogeneous, making it necessary to analyse an appropriate amount added to 10 mL vials containing PVC, PET, PA 6, ABS, PC, PUR, PP, LDPE, LLDPE and
of sediments. This usually requires a large amount of salt for density HPDE (10 particles between 0.5 and 1 mm and 10 particles between 2 and 3 mm)
and different biogenic organic matter of either animal or plant tissue commonly
separation. In the course of developing the method, emphasis was
found in beach sand samples, e.g. pieces of bone, chitin carapaces, feathers and
therefore placed on decreasing the sediment sample mass in the pieces of different plant tissues such as seed capsules, fruits, leafs and stems (16
first step to enable the economic use of NaI in the second step. In particles between 0.5 and 1 mm and 10 particles between 2 and 3 mm). The vials
addition, different solvents for dissolving biogenic matter were were then closed. The particles were exposed to a 30% solution of H2O2 for seven
tested. The two-step extraction method was applied to sediment days. Optical changes were noted for each particle immediately after adding the
solvent, and thereafter every 24 h. Optical changes were observed using a stereo-
samples from the island of Norderney, located off the German
microscope (Wild M3Z Leica Microsystems, Wetzlar, Germany). The intention was to
North Sea coast. Extracted particles were analysed using pyrolysis test how long it would take for all biogenic particles in the respective size class to
gas chromatography/mass spectrometry (Pyr-GC/MS) to identify disappear and to determine whether plastic particles would demonstrate resistance.
the types of polymer found. In the second series of tests, 4 ml NaOH and HCl, respectively, were added to
different particles of biogenic organic matter such as parts of leafs and chitin cara-
paces (four particles between 0.5 and 1 mm and 10 particles between 2 and 3 mm)
2. Materials and methods stored in 10 ml vials. These experiments were performed on a small scale compared
to those involving H2O2 described above, because it sufficed for an approximate
2.1. Chemicals and materials comparison to be made of the three reagents. HCl was only used in a concentration
of 20% because it has been reported that many polymers are not resistant to it in a
In order to prepare a saturated NaCl solution, common food-grade table salt higher concentration (Bürkle, 2010; Amsler and Frey, 2012). The experimental test
(Suedsalz GmbH, Heilbronn, Germany) containing small amounts of sodium ferro- conditions for HCl and NaOH were identical to those for H2O2 described above.
cyanide as an anticaking agent was diluted in distilled water. NaI (grade
99.5%) and A third experiment was performed using 4 mL of a 35% H2O2 solution in reaction
a 30% stabilised hydrogen peroxide (H2O2) solution were purchased from Sigma with various biogenic organic matter (13 particles between 0.5 and 1 mm and 10
Aldrich (Steinheim, Germany). Solutions of 35% stabilised H2O2 and of 37% hydro- particles between 2 and 3 mm). Likewise, 12 plastic particles in two size classes
chloric acid (HCl) (technical grade) were purchased from AppliChem (Darmstadt, (<1 mm and between 1 and 5 mm) of the most common polymer materials (PVC, PP,
Germany). The latter was diluted to a concentration of 20% by adding distilled water.
Solutions of sodium hydroxide (NaOH) with concentrations of 20, 30, 40 and 50%
were prepared by dissolving NaOH pellets (AppliChem, Darmstadt, Germany) in
distilled water.
Table 1
In order to perform recovery experiments, plastic particles of approximately
Polymer types, colours, products and sources of plastic particles used for recovery
1 mm in size were produced by cutting plastic products made of polyethylene (PE),
experiments (PE: polyethylene, PP: polypropylene, PVC: polyvinyl chloride, PET:
polypropylene (PP), polyvinyl chloride (PVC), polyethylene terephthalate (PET),
polyethylene terephthalate, PS: polystyrene, EPS: expanded PS, PUR polyurethane).
polystyrene (PS), expanded PS (EPS) and polyurethane (PUR) (see Fig. 1). The types of
polymer from all of the products were specified by referring to the respective Polymer Colour Original product Source
recycling code. The particles and their origin are described in Table 1. type
Plastic pellets and raw plastic materials were used (Table 2) to test 12 different
polymer types such as PVC, PET, polyacrylate, acrylnitrile-butadiene-styrene (ABS), PE Red Plastic laboratory Lab inventory
polycarbonate (PC), PUR, PE, PP, low-density PE (LDPE), linear LDPE (LLDPE), high- bottle
density PE (HPDE) and expanded PS (EPS) for resistance against H2O2, NaOH and PP Blue GC vial cap Lab inventory
HCl. PVC Orangeebrown Pipe Local hardware store
PET Green Water bottle Local discounter
PS Yellow/white Yoghurt cup Local discounter
2.2. Tests for eliminating biogenic organic matter EPS White StyrofoamÒ Lab inventory
packaging
Different solvents (H2O2, NaOH, HCl) were tested to dissolve biogenic matter of PUR Yellow Raw material KTK Kunststofftechnik
animal and plant origin. Simultaneous experiments were performed to test the Germering (Germany)
resistance of common polymers. In the first test, 4 ml of a 30% H2O2 solution was
 M.-T. Nuelle et al. / Environmental Pollution 184 (2014) 161e169 163

Table 2 the total extraction procedure. Two procedural blank samples were extracted as
Polymer names and types and supplier of plastic particles used for resistance ex- described in Sections 2.4 and 2.5, one (blank 1) using a four times reused NaCl so-
periments (PE: polyethylene, LDPE: low-density polyethylene, HDPE: high-density lution for pre-extraction (see Section 2.4) and the other (blank 2) using a newly
polyethylene, LLDPE: linear LDPE, PVC: polyvinyl chloride, PC: polycarbonate na- prepared NaCl solution to test for a higher background contamination risk from
ture, PA: polyamide, ABS: acrylnitrile-butadiene-styrene, PET: polyethylene tere- reusing the NaCl solution.
phthalate, PP: polypropylene, PS: polystyrene).
2.4. Fluidisation (first extraction step)
Polymer name/ Polymer type Supplier
product
Seeking to avoid background contamination, the following preventive measures
PE laboratory PE Lab inventory were taken during the extraction procedure: all materials and vessels used for the
bottle first time for one sample were cleaned in the dish washer if possible, or otherwise
LDPE 1840D LDPE (pellet) LyondellBasell Industries AF S.C.A., thoroughly by hand, and covered with aluminium foil immediately after washing
Rotterdam, the Netherlands them. Lab coats were worn at all times during analysis; all materials and vessels
HDPE ACP HDPE (pellet) LyondellBasell Industries AF S.C.A. were covered with aluminium foil after each individual step; and the workplace for
9255plus Rotterdam, the Netherlands stereomicroscopic analysis was cleaned before opening and analysing the petri
LLDPE 2049E LLDPE (pellet) Dow Plastics, Midland, USA dishes in which microplastics were stored.
Raw material PVC KTK Kunststofftechnik GmbH, Microplastics were extracted from sediment samples by applying a two-step
Germering, Germany extraction procedure. The basic idea was to use a combination of fluidisation of
Raw material PC KTK Kunststofftechnik GmbH, sediments in a lower density salt followed by flotation of microplastics in a higher
Germering, Germany density salt. First, the air-induced overflow (AIO) method was developed to pre-
Raw material PUR KTK Kunststofftechnik GmbH, extract sediments by fluidisation using a saturated NaCl solution. The aim of
Germering, Germany this first step was to decrease the sediment sample mass for the second density
Raw material PA KTK Kunststofftechnik GmbH, separation step by flotation. The principle of the AIO method is shown in Fig. 2. In
Germering, Germany order to prepare a saturated NaCl solution (26% weight/weight) with a density of
Raw material ABS KTK Kunststofftechnik GmbH, 1.2 g/cm3 (Schäfer and Synowietz, 1984), NaCl (food-grade table salt) was dis-
Germering, Germany solved in distilled water. A 2 L glass beaker was placed inside a glass vessel
Raw material PET KTK Kunststofftechnik GmbH, (25  30 cm). Approximately 1.5 L from the 6.5 L of saturated NaCl solution was
Germering, Germany pumped from a glass storage tank into the 2 L glass beaker using an indoor
PPHC 904 CF PP (pellets) Borealis AG, Vienna, Austria fountain pump (Gardena, Ulm, Germany). The pump was then stopped, and
PS 143E PS (pellets) BASF SE, Ludwigshafen, Germany moderate bubbling was generated by a constant air flow (air flow rate of
approximately 0.1 L/s) introduced into the NaCl solution. The sediment sample
(1 kg) was added quickly to the NaCl solution. The air-generated turbulent gas
bubbles induced a stochastic process that forced specific lighter particles to move
LDPE, PE, HDPE, PET, PUR, PS, PC, PA, ABS and EPS) were prepared as described more frequently and quickly to the top layer of the solution than specifically
above. All particles were photographed using a digital camera coupled to the ste- heavier ones. The remaining NaCl solution was pumped into the beaker with a
reomicroscope in a specified position. The surface area of each particle was deter- constant flow rate of about 2.4 L/min, inducing an overflow of the top layer into
mined using “Image J”, an image-processing program. After seven days, particles the outer glass vessel. Once 4 L of the NaCl solution had been transferred, the air
that had not dissolved fully were extracted from the solutions using tweezers and flow rate was increased to approximately 0.2 L/s. The overflowing mixture of NaCl
photographed again using the digital camera coupled to the stereomicroscope (Wild solution and floating particles was collected in the outer glass vessel (see Fig. 2).
M3Z Leica Microsystems, Wetzlar, Germany) in the same position. The surface area After the separation process, a series of thorough rinsing steps was performed to
of each particle was determined again and compared to the previous surface area. rinse the beaker with the saturated NaCl solution, which was then collected in the
outer vessel. The aim of applying numerous rinsing steps was to ensure the effi-
2.3. Sediment sampling and sample preparation cient transfer of plastic particles from the beaker to the outer vessel. The beaker
was rinsed in several steps using a saturated NaCl solution filled in a wash bottle:
On 2 November 2011, three sediment samples were taken from a beach on the first of all, the outer upper edge of the beaker was rinsed to remove any potential
northern side of the island Norderney, which is about 14 km long and 2.5 km wide. microplastics that had adhered to the outer wall. The beaker was then lifted by
Norderney is one of the eastern Frisian Islands, located on the German coast of the holding it by the previously cleaned upper edge of the vessel; the NaCl super-
North Sea. Norderney is heavily influenced by tidal streams and periodic storm natant was decanted into the outer vessel. The bottom of the beaker was subse-
surges in spring and autumn, producing a high degree of sediment mobilisation. The quently rinsed from the outside while still being held by the upper edge. The
northern side of the island, which is part of Lower Saxony’s Wadden Sea National beaker was then put on a glass plate that was placed across the outer vessel
Park, is characterised by beaches with a width of more than 250 m, far away from the (sustained by two parallel metal rods and the edges of the outer vessel) and rinsed
urban area, which is concentrated in the western part of the island. The randomly inside and outside. In this way, any adherent particles were washed into the
chosen sampling sites were located in the ‘recreation zone’ (Zone III), containing the collecting vessel below. Finally, the glass plate was rinsed over the collecting
main tourist beach areas. The maximum distance between sampling sites was vessel. The original sediments that remained in the beaker were then discarded.
approximately 80 m. The coordinates were 53.722067 /7.243967 for sample 1.6u, Since it was too time consuming to directly transfer the total supernatant through
53.722383 /7.247033 for sample 2.6u and 53.722383 /7.247025 for sample 2.6 l. a filter paper, the supernatant in the outer vessel was then transferred stepwise
Approximately 3 kg sediments were taken randomly from a depth of about 3 cm and into a 25 mm stainless-steel sieve installed on a collecting pan with outlet using a
placed in precleaned brown glass bottles using a stainless steel spoon. The spoon stainless steel ladle (both Retsch, Haan, Germany). The ‘sieved’ NaCl solution was
was cleaned using sea water and lint-free paper between each sample. The bottles stored for reuse for a maximum of six subsequent runs. The residue in the sieve
were sealed and stored at room temperature in the laboratory until analysis. Next, containing sediments and microplastics was rinsed again with 250 ml distilled
2 kg wet sediments from each bulk sample was transferred to ceramic bowls, which water into the outer glass vessel. The residue was then decanted from the outer
were subsequently covered with aluminium foil. The bowls were placed in a drying glass vessel by thoroughly rinsing with about 800 ml NaCl solution onto a folded
oven at 60  C until the sediments had dried out. A total of 1 kg dry sediments filter paper placed in a glass funnel. The filter cake was additionally rinsed with
(approximately 600 ml) was weighed out and sieved through a 1 mm mesh. The 700 ml distilled water to clean sodium chloride from the sample material.
<1 mm fraction was further analysed for the presence of microplastics using the The filter was dried in an oven at 60  C for 12 h, after which the filter residue was
procedure described in Sections 2.4 and 2.5, with the exception that the sediment carefully added to a glass beaker (500 mL) using a stainless steel laboratory spoon
samples from Norderney did not undergo treatment with H2O2 because they con- (residues were thoroughly removed from the folded filter using the spoon).
tained only small quantities of biogenic material.
Ten samples of 1 kg aquarium sand (grain size 0.1e0.9 mm, Rosnerski Baustoffe, 2.5. Flotation (second extraction step)
Koenigslutter, Germany) were spiked with seven types of plastic particles (PE, PP,
PVC, PET, PS, EPS and PUR, see Fig. 1 and Table 1) in order to determine the recoveries The second extraction step was performed using the principle of the flotation
of different types of plastic particles for the total extraction procedure. Recoveries of lower density microplastics in a saturated NaI solution with a density of 1.8 g/
3
were determined for the two-step extraction procedure without (n ¼ 6) and cm (Schäfer and Synowietz, 1984). Different volumetric flasks (volumes 50e
including a step to remove organic matter (“oxidation” step) by using a solution of 200 mL) were used for this purpose. The volume of the volumetric flask was
35% H2O2 (n ¼ 4) (see Section 2.2). Recoveries were obtained by calculating the chosen according to the sediment mass resulting from the first extraction step.
plastic particles remaining on the filter. The independent two-sample t-test was The sediment sample was added to the volumetric flask, and a 60% (weight/
used to test for any significant difference between these two series of tests. weight) NaI solution was added to roughly three-quarters of the flasks. It turned
Two samples of 1 kg aquarium sand (grain size 0.1e0.9 mm, Rosnerski Baustoffe, out that it was important to ensure the NaI volume remained below the angle of
Koenigslutter, Germany) were used in order to determine the procedural blank of the belly of the volumetric flask to make sure that the content of the flask could be
164 M.-T. Nuelle et al. / Environmental Pollution 184 (2014) 161e169

Fig. 2. Experimental setup for the AIO method (first extraction step). A: laboratory stands, B, C: clamps, D: glass tube, E: laboratory fume, F: glass tube, G: indoor fountain pump, H:
storage tank for NaCl (25  25 cm), I: outer glass vessel (25  30 cm), J: inner glass beaker (2 L), K: double sockets with parallel metal rods.

mixed completely by shaking. The flask was shaken by hand for about 20 s and 2.6. Pyr-GC/MS analysis
then filled with NaI solution to the highest calibration mark. The flask was then
shaken again for approximately 10 s to limit the amount of minerals on the so- Extracted particles were analysed using Pyr-GC/MS by applying a Multipurpose
lution surface due to adhesion and surface tension. The flask was then filled with Sampler 2XL equipped with the thermal desorption system (TDS 3) (Gerstel, Muel-
NaI solution to 1 cm below the rim. After a settling time of 10 min, the super- heim, Germany). Pyrolysis GC is used to obtain structural information about mac-
natant was decanted into a 200 mL glass beaker up to about 1 cm below the angle romolecules by carrying out a GC/MS analysis of their thermal degradation products.
of the belly, enabling the suspension to be shaken again for 10 s. The procedure of Ten polymer types of the most common standard polymers (PVC, PC, PUR, PA, ABS,
shaking, refilling, shaking, refilling, sedimentation and decantation was replicated PET, LDPE/EVA, PP, PS and EVA, see Table 2) were also analysed using Pyr-GC/MS to
five times. The supernatant in the 200 mL glass beaker was subsequently poured obtain a pyrogram database. Details on the polymers, experimental conditions and
into a vacuum filtration unit using a nitrocellulose filter (0.45 mm pore width, Mili, resulting pyrograms are provided by Fries et al. (2013). Briefly, the particle was
China). The glass beaker was rinsed thoroughly with about 250 ml distilled water pyrolysed at 700  C for 60 s. The temperature of the transfer line was 350  C. In order
into the vacuum filtration unit. The filtered NaI solution was collected for reuse to separate and detect pyrolysis products, the TDS was interfaced to a gas chro-
and the filter was air-dried for further analysis. The filter in the vacuum filtration matograph (GC) 7890A coupled to a mass selective detector (MS) 5975C (both Agilent
unit was then washed with 750 ml more distilled water to remove any salt resi- Technologies, Santa Clara, USA). A 30 m HP-5MS capillary column (Agilent Technol-
dues from the filter. ogies, Santa Clara, USA) with an inner diameter of 250 mm and a film thickness of
If H2O2 was applied to eliminate biogenic organic particles from the filter cake, a 0.25 mm was used to achieve chromatographic separation. The GC oven was pro-
further filtration step involving passing the supernatant through a new filter was grammed from 40 to 180  C at 15  C/min and then to 300  C at 5  C/min, held for
tested to remove NaI from the filter. To this end, the filter cake was rinsed thoroughly 12 min. The carrier gas was helium (purity 5.0) with a vent flow of 60 mL/min. Mass
with about 75 ml distilled water into the 200 ml glass beaker. The content of the spectra of organic plastic additives (OPAs) and pyrolysis products were obtained by
glass beaker was filtered again by vacuum filtration through a new filter, and washed running the MS in full scan mode with a mass range between 10 and 600 amu. Py-
with approximately 500 ml distilled water to remove any residues of NaI. The filter rolysis products were identified by consulting the NIST05 mass spectra library.
was subsequently rinsed with about 20 ml of a 35% H2O2 solution into a glass beaker
and stored in the solution at room temperature for seven days.
Since some of the particles on the filter had stuck to the protruding upper edge 3. Results
of the top glass funnel of the vacuum filtration unit, these adhered particles were
rinsed carefully with a small amount of distilled water into a glass petri dish. Finally,
the filter was transferred to the second glass petri dish. The filtered NaI solution was 3.1. Removal of biogenic organic matter
collected for reuse, and the content of both petri dishes was air-dried for further
analysis and covered with aluminium foil. First, the results for the 30% H2O2 solution are presented. Con-
In addition, an investigation was carried out to ascertain whether a separatory cerning biogenic organic particles >1 mm, 50% (most of which was
funnel (with volumes of 0.25, 1 and 2 L) is applicable as a suitable alternative to
volumetric flasks. Sediments were taken from the 500 mL glass beaker and placed
of animal origin) had completely dissolved after seven days. The
in the separatory funnel, and the NaI solution was added to roughly three-quarters other 50% also demonstrated obvious reactions, i.e. they became
of the funnels. After shaking for approximately 10 s and following a settling time of discoloured or transparent, or had partly dissolved. Results for
10 min, the deposed sediments were drained off the funnel by opening the stop- biogenic particles <1 mm were similar (56% had dissolved
cock. Shortly before the sinking surface layer and the floating microplastics reached
completely while the other particles were either discoloured and/
the zone above the stopcock, the stopcock was instantaneously closed. As a
consequence, only the surface layer of the solution with the floating plastics or had partly dissolved). For all polymer types from both size
remained in the funnel. The content of the funnel was then filtered as described classes, a reaction was observed in that gas development occurred
above. to different extents. The experiment with polymer particles >1 mm
An optical analysis of the filters was performed using a stereomicroscope (Wild in size also showed visible changes for PA, PC and PP, which were
M3Z, Leica Microsystems, Wetzlar, Germany) providing 6.5-fold up to 40-fold
magnifications. Optical images of particles were taken using a digital camera,
more transparent, smaller and/or thinner after exposure. Definite
which was connected to the microscope via a phototube. Particles that were opti- optical changes were also determined for PET (brownish colour)
cally identified as potential plastics were separated using tweezers. and LLDPE (fragmented). For particles <1 mm, one range of
 M.-T. Nuelle et al. / Environmental Pollution 184 (2014) 161e169 165

polymers was slightly more transparent, thinner or smaller (PVC, Table 3

PET, PA, PUR, PP, LDPE, LLDPE). It was observed that PC was defi- Volumetric flask size and volume of NaI solution used for different sediment sam-
pling masses resulting from the first extraction step.
nitely thinner than before.
Results of the experiments involving NaOH and HCl revealed Volumetric flask size (ml) Sample mass (g) NaI consumption (ml)
that overall optical changes to biogenic organic particles were 50 <50 90
weaker than the reaction using 30% H2O2. None of the biogenic 100 50 170
organic particles had dissolved completely or become fully trans- 100 75 125
100 85 110e115
parent. A strong reaction was only observed with 30% NaOH and
200 100 255
20% HCl, respectively, with a beetle carapace. 200 125 215
The experiments involving the 35% H2O2 solution revealed that 200 150 200
each biogenic organic particle showed a visible, measurable reac- 200 175 190
200 200 195e200
tion, as with the particles exposed to the 30% H2O2 solution. The
outcome regarding biogenic organic particles >1 mm was that four
particles had dissolved completely, eight were transparent and one
was inconsistent. About 92% of particles had dissolved completely unpaired student’s t-test). The results demonstrated that additional
or were becoming discoloured. Regarding micro-particles (<1 mm), filtration and rinsing during the application of the oxidation step
25% had dissolved completely. Six particles were discoloured or had had no effect on extraction efficiencies. Thus mean recoveries were
become transparent, three had dissolved, two showed a consider- determined for all 10 runs. Mean recovery rates for PE, PP, PVC, PET,
able reduction in size and two were inconsistent. None of the PS, EPS and PUR ranged between 91% (relative standard deviation,
plastic particles showed a significant change in size, except for PP RSD: 0.4%) for PET and 99% (RSD: 3.0%) for PE. Only the extremely
and PE particles in the <1 mm size category, which showed a low dense EPS exhibited a lower recovery rate of 68% (RSD: 0.4%)
reduction in size of 17.2% and 15.9%, respectively. To test the (Table 4).
applicability of a treatment involving a 35% H2O2 solution using the
AIO/flotation method developed here, a beach sand sample 3.3. Background contamination
collected from the island of Fehmarn located in the Baltic Sea was
used since they contained large quantities of biological organic The results of the optical analysis of procedural blanks 1 and 2
material. Fig. 3 shows what the filter looked like after the two are shown in Fig. 4aed. Blank 1 contained 39 coloured fibres,
extraction steps had been taken before (Fig. 3a) and after (Fig. 3b) mainly blue and light blue, and red and black. A total of 33 coloured
having been treated with 35% H2O2. Treatment of the finally fibres, mainly blue, light blue and red, were extracted from blank 2.
extracted fraction on the filter with 35% H2O2 showed a visible The processing and storing of aquarium sand could not completely
effect compared to the non-treated one to the extent that the be ruled out as a source of these fibres. In addition, between three
treated filter contained visibly fewer biological organic particles and five fibres were found in each petri dish exposed to laboratory
that were completely bleached. air for five days with an optical appearance resembling that found
in the procedural blank samples.
3.2. Separating microplastics from sediments
3.4. Occurrence of microplastics in sediments from Norderney
During the first extraction step, the original sample mass of 1 kg
was reduced to values between 43.9 and 122.7 g by fluidisation of Optical images of five particles, which could potentially be
the sediments in a NaCl solution (see Table 4). Volumetric flask microplastics, are shown in Fig. 5. Two particles were found in
sizes (ml) and volumes of NaI solution recommended for different sample 1.6u (# 1, #2), one in sample 2.6u (#3) and two in sample 2.6 l
sediment sampling masses are shown in Table 3. For sediment (#4, #5). The following pyrolysis products were identified in the
sample masses between < 50 and 200 g, volumes of NaI solution pyrograms obtained by the Pyr-GC/MS analyses of particles #2 and
between <90 and 255 mL turned out to be sufficient. The NaI #5 and of a PET standard (the retention times, RT, for individual
volume and the volume of the volumetric flask had to be increased compounds are given in brackets): 1,2-propanedione-1-phenyl (RT:
in line with the sediment mass. 6.675 min), benzenecarboxylic acid (RT: 7.370 min), divinyl tere-
Recovery rates calculated for the total extraction procedure with phthalate (RT: 10.622 min), terephthalatic acid (RT: 11.064 min), 2-
and without the oxidation step using H2O2 are shown in Table 4. No (benzyloxy)ethyl vinyl terephthalate (RT: 25.145 min) and ethan-
significant differences were observed concerning recovery rates for 1,2-diyl divinyl diterephthalate (RT: 31.252 min). Several
any tested polymer types between the two series of tests (p > 0.05, terephthalate-based compounds are also described as pyrolysis
products for PET in Tsuge et al. (2011). A comparison of the pyrogram
of particle #3 with that obtained from the Pyr-GC/MS analysis of PVC
revealed a match of 13 major peaks, albeit with different relative
peak intensities. The following characteristic peaks were identified
(RT are given in brackets): o-xylene (RT: 3.989 min), p-xylene (RT:
4.223 min), napthalene (RT: 7.213 min), 1-methylnapthalene (RT:
8.312 min), 2-methylnapthalene (RT: 8.419 min), acenaphthene (RT:
9.976 min), fluorene (RT: 10.925 min) and anthracene (RT:
13.171 min). Hence, an original PVC-based polymer is likely. A
comparison of the pyrogram obtained from the pyrolysis of PP and
the transparent white particle #4 revealed that this particle was PP.
Important evidence for the presence of PP was the first peak, which
was identified as 2,4 dimethyl-1-heptene e a typical pyrolysis
product of PP (Tsuge et al., 2011). It was not possible to identify
Fig. 3. Biogenic matter on the filter of a beach sand sample from Fehmarn a) before particle #1 because there was no comparable type of pyrogram in
and b) after treatment with H2O2. the database of analysed polymer types.
166 M.-T. Nuelle et al. / Environmental Pollution 184 (2014) 161e169

Table 4
Recoveries for seven different polymer types from sediment samples (n ¼ 6 for two step-extraction, n ¼ 4 for two step-extraction including H2O2 oxidation of the material on
the filter) including mean recoveries (PE: polyethylene, PP: polypropylene, PVC: polyvinyl chloride, PET: polyethylene terephthalate, PS: polystyrene, EPS: expanded PS, PUR:
polyurethane, RSD: relative standard deviation). The given sample mass is the mass of sediments resulting from the first extraction step.

Run Reduced sample mass (g) Polymer type

PE PP PVC PET PS EPS PUR

Particles counted on the filter

1 74.1 10 8 10 10 9 9 10
2 78.1 10 10 10 10 10 3 10
3 87 10 10 10 9 10 8 10
4 43.9 10 9 10 8 10 5 10
5 74.9 10 10 10 10 8 10 10
6 122.7 10 10 10 9 7 7 10
Mean recovery rate without “oxidation 100 95 100 93.3 90 70 100
step” n ¼ 6 (%)
7 69.3 10 9 9 8 10 2 7
8 74 10 10 10 7 10 8 10
9 45.5 10 10 10 10 9 8 10
10 56.7 9 10 8 10 9 8 9
Mean recovery rate with “oxidation 97.5 97.5 92.5 87.5 95 65 90
step” n ¼ 4 (%)
Mean recovery rate n ¼ 10 (%) (SD) 99 (3.0) 96 (6.6) 97 (6.4) 91 (10.4) 92 (9.8) 68 (24.8) 96 (9.2)

All sediment samples collected from Norderney contained fibres substances whilst ensuring that plastics remain resistant to it. The
with a length from about 0.5 mm to a few centimetres, with a first step taken before testing a reagent was to verify and compare
diameter of less than 100 mm. These samples were divided into chemical resistance tables issued by plastics manufacturers. Some
coloured and uncoloured groups. The latter also contained black, polymers such as PET, PUR, PA and PC are reported to be non-inert
brown and beige fibres in addition to mainly translucent fibres to or only constrictively inert to H2O2, NaOH and HCl (Bürkle GmbH,
distinguish fibres of a probable natural origin from obviously col- 2010; Polydraack GmbH, 2006). However, tests under respective
oured fibres e mainly blue, red and green e where an artificial test conditions are recommended. Generally, concentrated acids
origin was more likely. The numbers of uncoloured and coloured and alkalis are known to destroy biological tissue by essentially
fibres were 213 and 21 in sample 1.6u, 55 and 14 in sample 2.6u, cleaving proteins, carbohydrates and fats. However, biogenic
and 194 and 10 in sample 2.6.l. organic particles were dissolved to a lower extent following the use
of NaOH and HCl than when H2O2 was applied. Consequently, H2O2
4. Discussion was used for further processing. A 30% H2O2 solution was found to
be the ideal reagent for deleting about 50% of biogenic organic
4.1. Removing biogenic organic matter matter, However, a number of visible changes in some polymers
were also observed, including the development of gas bubbles,
The task was to define an appropriate reagent and reaction indicating a chemical reaction between H2O2 and the polymers. The
conditions that cause the effective deletion of biogenic organic optical analysis of polymers before and after exposure to H2O2 was

Table 5
Densities of polymer types, and European demand for commonly used polymers, densities of minerals mainly present in sediments, and densities of saturated salt solutions
used in this study (w/w: weight/weight).

Polymer Polymer name European demand Density [g/cm3] Density with Mineral Density [g/cm3] Salt solution Density [g/cm3]
abbr. [%] (Plastics Europe, (US EPA, 1992) Additive [g/cm3] (Matthes, 2001) (saturated) (Schäfer and
2010) (US EPA, 1992) Synowietz, 1984)

HDPE High-density 12 0.94e0.97 1.18e1.28 (PE) Quartz 2.65 NaCl (26% w/w) 1.2
polyethylene
LDPE Low-density 17 0.89e0.94 Potassium 2.56 NaI (60% w/w) 1.8
polyethylene, Feldspar
PP Polypropylene 19 0.89e0.91 1.04e1.17 Light Mica 2.80
PVC Polyvinylchloride 11 1.3e1.58 1.3e1.7 Magnetite 5.2
PET Polyethylene 8 1.29e1.40 Calcite 2.7
terephthalate
PS Polystyrene 8 (incl. PS-E) 1.04e1.08 1.2e1.5
EPS Expanded 0.015e0.03a
polystyrene
PA Polyamide 2.3 1.07e1.08 1.13e1.62
PC Polycarbonate 1.2 1.20
PMMA Polymethyl- 0.9 1.17e1.20
(acrylic) methacrylate
SAN Styrolacrylnitrile 1.9 (incl. ABS) 1.02e1.08
ABS Acrylonitrile/ 1.01e1.08 1.18e1.61
butadiene/
styrene
PUR Polyurethane 7 1.17e1.28
a
BASF SE (2011).
 M.-T. Nuelle et al. / Environmental Pollution 184 (2014) 161e169 167

Fig. 4. Fibres extracted from procedural blank 1 (a, b) and procedural blank 2 (c, d).

found to be insufficient for evaluating the resistance of polymers to area calculations apparently caused significant measurement in-
H2O2. In contrast, it emerged that calculating the reduction in accuracy. This could be seen in the frequent positive values for the
surface areas of polymers before and after exposure was an change in surface area. Since an increase in particle size due to
appropriate tool for determining their resistance to a solution of reaction with H2O2 is unlikely, the positive values act as an indi-
35% H2O2. However, it must be mentioned that applying the surface cator of the magnitude of measuring error. Thus an absolute

Fig. 5. Microplastics extracted from sediments collected at Norderney (a: sample 1.6u, b: sample 2.6u, c: sample 2.6 l). The scale bar at the bottom is divided into 100 mm markings
(the length between elongated markings is 1 mm).
168 M.-T. Nuelle et al. / Environmental Pollution 184 (2014) 161e169

measurement error was estimated from the mean of positive values reported in Claessens et al. (2011), using the method of Thompson
for surface change, amounting to 6.2% for particles of <1 mm in size et al. (2004) with a number of minor modifications, ranged from
and 2.5% for particles of >1 mm in size. When taking this into ac- 68.8% to 97.5% (no information is given on recoveries for particular
count, the reduction in size of PP and PE particles <1 mm was polymer types). Imhof et al. (2012) achieved a mean recovery rate
approximately 10%. Together with the fact that PP and PE exhibited of 95.5  1.8% for 0.1 g microplastic particles from seven environ-
no considerable change in size in the >1 mm size class, these re- mentally relevant plastic types (PA, PE, PVC, PC, HDPE, PET, and PP)
sults could be interpreted as a minimal change in PP and PE in with a diameter <1 mm in 1 L sediments using a ZnCl2 solution.
contact with H2O2. In summary, a week-long treatment using a 35% A solution of NaCl (Thompson et al., 2004; Browne et al., 2010)
H2O2 solution is suitable for removing biogenic organic particles or tap water (Zurcher, 2009) was used to separate microplastics
whilst ensuring that all tested polymer types are resistant to it. The from sediments by flotation of lighter particles on the solution
results of the present study show that the remaining particles surface. The use of NaCl for flotation is also recommended in the
became discoloured, i.e. white or transparent, after H2O2 treatment. tool sheet for analysing microplastics in technical recommenda-
Since other studies report that microplastics found in marine sed- tions for implementing MSFD (JRC, 2011). One advantage of NaCl is
iments are often naturally coloured white or transparent (reviewed that it is a relatively inexpensive salt, and also eco-friendly. How-
in Hidalgo-Ruz et al., 2012), it must be mentioned that H2O2 could ever, the maximum density achieved using a saturated NaCl solu-
also complicate optical analysis rather than facilitate it, since nat- tion is only 1.2 g/cm3. Several common polymers such as PET, PVC,
ural particulates can then no longer be distinguished from plastics and PUR, as well as HDPE, PS, PA and ABS, which contain additives
that are whitish or transparent. To conclude, the oxidation step (US EPA, 1992), exceed this density (see Table 5 for an overview of
during analysis is only recommended if there is a large amount of the density ranges of common polymers, common minerals in
organic matter on the filter comprising almost a layer of particles, sediments and saturated solutions of NaCl and NaI). The density of
making visual selection impossible. It is therefore recommended lighter polymers can be enhanced by the presence of additives,
that this “oxidation step” is not applied routinely in the extraction fillers or bio fouling processes (US EPA, 1992; Braun, 2003;
procedure, but should be determined on a case-by-case basis for Thompson et al., 2009; Moret-Ferguson et al., 2010; Hidalgo-Ruz
each sample, depending on the quantity of biogenic matter ob- et al., 2012). The use of NaCl or tap water may therefore lead to
tained in the filter following extraction. In contrast to Liebezeit and an underestimation of the microplastic content in sediments
Dubaish (2012), it is also recommended to expose filters to H2O2 because the solution density is too low to enable their flotation.
instead of the whole original sediment sample, since it may be Instead, the density of the saturated NaI solution used in the pre-
difficult to treat 1 kg sediments. Since iodide ions act as catalysts, sent study is high enough to separate common polymers (including
causing an undesirable decomposition of H2O2 into water and ox- those containing additives) from higher density minerals (Table 5).
ygen, a reaction of NaI and H2O2 must be avoided by all means. The However, two-step extraction is more time consuming than flota-
reaction is extremely exothermic, and causes strong gas develop- tion using NaCl only. It was previously assumed that only lower
ment. After having conducted a few trials, it became evident that density plastic particles with the capability of floating in sea water
residues of NaI can only be eliminated fully by additional filtration are present in beach sediments (Zurcher, 2009), which would mean
and rinsing through a new filter. that it would suffice to use only NaCl. However, it must be
mentioned that higher density sediments and debris (Liebezeit,
4.2. Separating microplastics from sediments 2008; OSPAR, 2009; Browne et al., 2010) are also washed ashore.
Consequently it must be assumed that the entire range of polymer
Our results demonstrate the importance of performing blank types can potentially occur as microplastics in sediments on
samples to obviate overestimations of microplastic pollution of shorelines (Moret-Ferguson et al., 2010). Since high-density
marine sediments when taking microplastic fibres into account. microplastics are present in beach sediments, flotation in a high-
From our experience gained whilst developing the method, we density solution is necessary to extract polymers of a broad den-
assume that extraction methods for microplastics in general are sity range. However, it must be said here that Browne et al. (2010)
highly susceptible, particularly to background contamination by also extracted PVC from sediments using an NaCl solution for
fibres from the working environment. Since fibres contained in extracting microplastics from sediments.
samples were optically very similar to those found in procedural As with all other higher density salts, NaI is a relatively
blanks (Fig. 4), contamination of samples with fibres must be expensive salt. In contrast to previously described methods
avoided by all means during sampling and analysis. The sources of involving large volumes of high-density salts (Imhof et al., 2012) or
fibre background contamination were not proven. It was found that smaller sample masses (Corcoran et al., 2009; Liebezeit and
recycling the NaCl solution had no significant impact on back- Dubaish, 2012), we managed to reduce the volume of NaI solu-
ground contamination. The problem of fibre background contami- tion by reducing the original sediment mass in the first extraction
nation has been touched upon in the past (Fries et al., 2013), and a step. A relatively high sample amount of 1 kg enables a higher
comparison of background contamination levels among labora- statistical relevance to be achieved when extrapolating from
tories was urgently recommended by Hidalgo-Ruz et al. (2012). random samples to the overall test area. By applying our meth-
However, it is likely to be difficult to find appropriate sediments odology, the analytical cost of extracting microplastics from sedi-
that are free of fibres for running the procedural blank. ments is cut remarkably, which is important for a routinely
By applying the two-step separation method, it was possible to applicable monitoring method for microplastics in sediments. In
efficiently extract common polymers of about 1 mm in size from addition, according to the German Water Hazard Classification
1 kg sediments. Recovery rates can be fed as correction factors into (WGK), higher density salts such as ZnCl2 and polytungstate which
evaluations of environmental sample analyses, as suggested by have been used in the past (Corcoran et al., 2009; Imhof et al.,
Claessens et al. (2011). Since EPS had the lowest density of those 2012; Liebezeit and Dubaish, 2012) are “severely hazardous to
polymers tested, its lower recovery rate may be attributed to loss waters” (WGK3) and “hazardous to waters” (WGK2), respectively,
processes other than flotation. A loss of EPS was observed due to its whereas NaI poses only a “minor threat to waters” (WGK1) (Sigma
strong adherence behaviour to glass surfaces. Up to now, recovery Aldrich, product data sheets). An additional benefit of the AIO/
rates for extracting microplastics from sediments have only rarely flotation method presented here is that all materials used are
been reported. The recovery rates of fibres and granules/spheres available in any conventional lab setting and that no extra
 M.-T. Nuelle et al. / Environmental Pollution 184 (2014) 161e169 169

apparatus needs to be constructed, which is the case for the Andrady, A.L., 2011. Microplastics in the marine environment. Mar. Pollut. Bull. 62,
1596e1605.
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BASF SE, 2011. Technical data sheet e StyroporÒF 295-N (in German). Ludwigshafen,
In previous studies, separatory funnels were often used for Germany.
flotation (e.g. Thompson et al., 2004; Browne et al., 2010). In the Braun, D., 2003. Kunststofftechnik für Einsteiger. Carl Hanser, München (in German).
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Corcoran, P.L., Biesinger, M.C., Grifi, M., 2009. Plastics and beaches: a degrading
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The two-step extraction method enabled microplastics to be
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