Field and mesocosm methods to test biodegradable plastic film under marine conditions.

The pollution of the natural environment, especially the world's oceans, with conventional plastic is of major concern. Biodegradable plastics are an emerging market bringing along potential chances and risks. The fate of these materials in the environment and their possible effects on organisms and ecosystems has rarely been studied systematically and is not well understood. For the marine environment, reliable field test methods and standards for assessing and certifying biodegradation to bridge laboratory respirometric data are lacking. In this work we present newly developed field tests to assess the performance of (biodegradable) plastics under natural marine conditions. These methods were successfully applied and validated in three coastal habitats (eulittoral, benthic and pelagic) and two climate zones (Mediterranean Sea and tropical Southeast Asia). Additionally, a stand-alone mesocosm test system which integrated all three habitats in one technical system at 400-L scale independent from running seawater is presented as a methodological bridge. Films of polyhydroxyalkanoate copolymer (PHA) and low density polyethylene (LD-PE) were used to validate the tests. While LD-PE remained intact, PHA disintegrated to a varying degree depending on the habitat and the climate zone. Together with the existing laboratory standard test methods, the field and mesocosm test systems presented in this work provide a 3-tier testing scheme for the reliable assessment of the biodegradation of (biodegradable) plastic in the marine environment. This toolset of tests can be adapted to other aquatic ecosystems.

Magnetic solid-phase extraction based on magnetic carbon particles from coffee grounds for determining phthalic acid esters in plastic bottled water.

Newly developed magnetic carbon particles prepared from coffee grounds were used as the sorbent for the magnetic solid-phase extraction of eight phthalic acid esters (PAEs) from plastic bottled water prior to their analysis by GC-MS. The method, which uses coffee-ground particles coated with iron oxide, was validated, and exhibited linearities for the eight PAEs, with coefficients of determination above 0.998 in the 0.005 to 0.1 mg/L concentration range. Limits of detection and limits of quantification of 0.00003 to 0.002 mg/L and 0.0001 to 0.005 mg/L, respectively, were achieved, with recoveries (%) ranging between 77% and 120%, and relative standard deviations for intra- and interday precisions below 16.3% at three fortification levels. No PAE residues were detected when the developed and validated method was applied to 10 real plastic bottled water samples. Taken together, the developed magnetic solid-phase extraction method is a useful tool for monitoring phthalate esters in aqueous samples. PRACTICAL APPLICATION: The development of a new, inexpensive, and efficient magnetic sorption material derived from spent coffee grounds, and its ability to determine phthalate esters in aqueous solutions was described by GC-MS/MS. The developed magnetic solid-phase extraction method is a useful tool for monitoring phthalate esters in aqueous samples.

Microplastics in the wastewater treatment plants (WWTPs): Occurrence and removal.

WWTPs may be one of the important ways for MPs to enter surface water. In the present study, the influent and effluent from eleven WWTPs in Changzhou were collected and analyzed. At the same time, the abundance, size, color, and shape of MPs in influent and effluent were investigated. The average abundance of MPs in the influent and effluent were 196.00 ±â€¯11.89 n/L and 9.04 ±â€¯1.12 n/L respectively, and the MPs removal efficiency of eleven WWTPs was almost over 90% in which it could be up to 97.15%. MPs were divided into four particle size based on abundance changes, and the size of MPs with the highest abundant was mainly concentrated at 0.1-0.5 mm. Among these MPs, fibers were the main shape in wastewater, followed by fragments, flakes, spheres and films. The colors of MPs in wastewater were various and 14 types of plastics were detected from wastewater using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR). Moreover, Rayon and PET were the dominant polymer types in eleven WWTPs. The research results provided basic data for the research and supervision of MPs pollution in WWTPs.

A study on characteristics of microplastic in wastewater of South Korea: Identification, quantification, and fate of microplastics during treatment process.

This study investigated the removal of microplastics from different treatment stages in three WWTPs and examined the performance of tertiary treatment that was done by coagulation and different technologies such as ozone (WWTP-A), membrane disc-filter (WWTP-B), and rapid sand filtration (WWTP-C). The results showed that the primary and secondary treatment processes effectively remove microplastics from wastewater with efficiencies ranging between 75% and 91.9%. The removal efficiency increased further to >98% after tertiary treatment. Microbeads and fragments were the major types of microplastics found in all wastewater sampling points. Microbeads found in the wastewater samples were classified as primary microplastics, that mainly came from personal care products, whereas secondary microplastics consisted of fragments, fibers, and sheets that were generated mainly due to fragmentation of larger plastics. Microplastics were still found in a high concentration in the final effluent, especially from WWTP-B, which is discharged into the Geumho river.

An efficient and gentle enzymatic digestion protocol for the extraction of microplastics from bivalve tissue.

Standardized methods for the digestion of biota for microplastic analysis are currently lacking. Chemical methods can be effective, but can also cause damage to some polymers. Enzymatic methods are known to be gentler, but often laborious, expensive and time consuming. A novel tissue digestion method with pancreatic enzymes and a pH buffer (Tris) is here presented in a comparison to a commonly applied digestion protocol with potassium hydroxide. The novel protocol demonstrates a highly efficient removal of bivalve tissue (97.7 ±â€¯0.2% dry weight loss) already over-night. Furthermore, it induces no impairment in terms of ability to correctly identify four pre-weathered plastic polymers and six textile fiber polymers by Fourier transform infrared spectroscopy after exposure. The high-throughput protocol requires minimal handling, is of low cost and does not pose risk to the performer or the environment. It is therefore suggested as a candidate for a standardized digestion protocol, enabling successful analysis of microplastics ingested by bivalves.

Evaluation of existing methods to extract microplastics from bivalve tissue: Adapted KOH digestion protocol improves filtration at single-digit pore size.

Methods standardisation in microplastics research is needed. Apart from reagent-dependent effects on microplastics, varying target particle sizes can hinder result comparison between studies. Human health concerns warrant recovery of small microplastics. We compared existing techniques using hydrogen peroxide, Proteinase-K, Trypsin and potassium hydroxide to digest bivalve tissue. Filterability, digestion efficacy, recoverability of microplastics and subsequent polymer identification using Raman spectroscopy and a matching software were assessed. Only KOH allowed filtration at ≤25 µm. When adding a neutralisation step prior to filtration, KOH digestates were filterable using 1.2-µm filters. Digestion efficacies were >95.0% for oysters, but lower for clams. KOH destroyed rayon at 60 °C but not at 40 °C. Acrylic fibre identification was affected due to changes in Raman spectra peaks. Despite those effects, we recommend KOH as the most viable extraction method for exposure risk studies, due to microplastics recovery from bivalve tissues of single-digit micrometre size.

Mediated food and hydrodynamics on the ingestion of microplastics by Daphnia magna.

There is consensus on the need to study the potential impact microplastics (MP) have on freshwater planktonic organisms. It is not yet fully understood how MP enter the aquatic food web or the effect they have on all the trophic levels. As a result of the potential for MP to accumulate throughout food webs, there is increasing interest in evaluating their fate in a variety of environmental conditions. This study investigated the variability in the ingestion of MP to food ratios and the exposed time of MP to Daphnia magna in non-sheared and sheared conditions. The sheared environment provided Daphnia magna with the conditions for optimal filtering capacity. Regardless of the ratios of MP concentration to food concentration (MP:Food), the filtration capacity of the Daphnia magna was enhanced in the sheared experiments. In both the sheared and non-sheared experiments, filtration capacity decreased when the ratios of MP to food concentration and the exposure times to MP were increased. Mortality was mainly enhanced in the non-sheared conditions at higher MP concentrations and exposure times to MP. No mortality was found in the sheared conditions for the exposure times studied. Therefore, in aquatic systems that undergo constant low sheared conditions, Daphnia magna can survive longer when exposed to MP than in calm conditions, provided food concentrations do not limit their capacity to filter.

Separation and Analysis of Microplastics and Nanoplastics in Complex Environmental Samples.

The vast amount of plastic waste emitted into the environment and the increasing concern of potential harm to wildlife has made microplastic and nanoplastic pollution a growing environmental concern. Plastic pollution has the potential to cause both physical and chemical harm to wildlife directly or via sorption, concentration, and transfer of other environmental contaminants to the wildlife that ingest plastic. Small particles of plastic pollution, termed microplastics (>100 nm and <5 mm) or nanoplastics (<100 nm), can form through fragmentation of larger pieces of plastic. These small particles are especially concerning because of their high specific surface area for sorption of contaminants as well as their potential to translocate in the bodies of organisms. These same small particles are challenging to separate and identify in environmental samples because their size makes handling and observation difficult. As a result, our understanding of the environmental prevalence of nanoplastics and microplastics is limited. Generally, the smaller the size of the plastic particle, the more difficult it is to separate from environmental samples. Currently employed passive density and size separation techniques to isolate plastics from environmental samples are not well suited to separate microplastics and nanoplastics. Passive flotation is hindered by the low buoyancy of small particles as well as the difficulty of handling small particles on the surface of flotation media. Here we suggest exploring alternative techniques borrowed from other fields of research to improve separation of the smallest plastic particles. These techniques include adapting active density separation (centrifugation) from cell biology and taking advantage of surface-interaction-based separations from analytical chemistry. Furthermore, plastic pollution is often challenging to quantify in complex matrices such as biological tissues and wastewater. Biological and wastewater samples are important matrices that represent key points in the fate and sources of plastic pollution, respectively. In both kinds of samples, protocols need to be optimized to increase throughput, reduce contamination potential, and avoid destruction of plastics during sample processing. To this end, we recommend adapting digestion protocols to match the expected composition of the nonplastic material as well as taking measures to reduce and account for contamination. Once separated, plastics in an environmental sample should ideally be characterized both visually and chemically. With existing techniques, microplastics and nanoplastics are difficult to characterize or even detect. Their low mass and small size provide limited signal for visual, vibrational spectroscopic, and mass spectrometric analyses. Each of these techniques involves trade-offs in throughput, spatial resolution, and sensitivity. To accurately identify and completely quantify microplastics and nanoplastics in environmental samples, multiple analytical techniques applied in tandem are likely to be required.

Bioplastic recovery from wastewater: A new protocol for polyhydroxyalkanoates (PHA) extraction from mixed microbial cultures.

A new protocol for polyhydroxyalkanoates (PHA) extraction from mixed microbial cultures (MMCs) is proposed. PHA-accumulating capacity of the MMC was selected in a sequencing batch reactor (SBR) fed with a synthetic effluent emulating a fermented oil mill wastewater (OMW). The highest recovery yield and purity (74 ±â€¯8% and 100 ±â€¯5%, respectively) was obtained when using NH4-Laurate for which operating conditions of the extraction process such as temperature, concentration and contact time were optimized. Best conditions for PHA extraction from MMC turned to be: i) a pre-treatment with NaClO at 85 °C with 1 h of contact time, followed by ii) a treatment with lauric acid in a ratio acid lauric to biomass of 2:1 and 3 h of contact time.

Poor extraction efficiencies of polystyrene nano- and microplastics from biosolids and soil.

Extraction and quantification of nano- and microplastics from sediments and soils is challenging. Although no standard method has been established so far, flotation is commonly used to separate plastic from mineral material. The objective of this study was to test the efficiency of flotation for the extraction of nano- and microplastics from biosolids and soil. We spiked biosolids and soil samples with polystyrene nano- and microbeads (0.05, 1.0, 2.6, 4.8, and 100 µm diameter). Different extraction methods (w/ and w/o H2O2 digestion) were tested, and plastic beads were separated from mineral particles by flotation in a ZnCl2 solution. Plastic particles were quantified by UV-Vis spectrometry and gravimetrically. While large beads (100 µm) could be quantitatively extracted (∼100%) from both biosolids and soils, smaller beads had low extraction efficiencies (ranging from 5 to 80%, with an average of 20%). Except for the 100 µm beads, oxidation with H2O2 negatively impacted the extraction efficiencies. For the soil, extraction with water only, followed by flotation in a ZnCl2 solution, resulted in relatively high extraction efficiencies (>75%) for beads larger than 1 µm, but low efficiencies (<30%) for the 0.05 and 1.0 µm beads. Our results indicate that while flotation generally works to separate plastic nano- and microbeads in a solution, the challenge is to quantitatively extract nano- and microbeads from a biosolids or soil matrix. Samples high in organic matter content require removal of the organic matter, but the common method of H2O2 oxidation leads to poor extraction efficiencies for nano- and microbeads.

Novel methodology to isolate microplastics from vegetal-rich samples.

Microplastics are small plastic particles, globally distributed throughout the oceans. To properly study them, all the methodologies for their sampling, extraction, and measurement should be standardized. For heterogeneous samples containing sediments, animal tissues and zooplankton, several procedures have been described. However, definitive methodologies for samples, rich in algae and plant material, have not yet been developed. The aim of this study was to find the best extraction protocol for vegetal-rich samples by comparing the efficacies of five previously described digestion methods, and a novel density separation method. A protocol using 96% ethanol for density separation was better than the five digestion methods tested, even better than using H2O2 digestion. As it was the most efficient, simple, safe and inexpensive method for isolating microplastics from vegetal rich samples, we recommend it as a standard separation method.

Magnetic solid-phase extraction based on magnetic zeolitic imazolate framework-8 coupled with high performance liquid chromatography for the determination of polymer additives in drinks and foods packed with plastic.

In this study, magnetic zeolitic imazolate framework-8 (Fe3O4@ZIF-8) was successfully synthesized by a typical hydrothermal method. The facile magnetic solid-phase extraction (MSPE) based on Fe3O4@ZIF-8 was proposed for concentrating polymer additives (antioxidants and ultraviolet absorbers). The conditions of MSPE process were optimized. An analytical method of magnetic solid-phase extraction followed by high performance liquid chromatography (MSPE-HPLC) was successfully established for the simultaneous determination of seven polymer additives in drinks and foods packed with plastic. The established method showed good precision, reproducibility, stability, and accuracy with the low limits of detection (0.03-0.15 ng/mL) and limits of quantification (0.08-0.50 ng/mL). The results of this study indicated the Fe3O4@ZIF-8 coupled with HPLC provided an efficient enrichment and determination method for polymer additives in drinks and foods.

Microplastic in beach sediments of the Isle of Rügen (Baltic Sea) - Implementing a novel glass elutriation column.

To extent the understanding on microplastics in the marine environment we performed a case study at four beaches on the Isle of Rügen considering abundance and spatial distribution of microplastics in beach sediments. For the analysis, density separation via a glass elutriation column was implemented. In advance, efficiencies were tested for two polymers, being not buoyant in water. Recovery rates of 80% for PET and 72% for PVC particles in sandy samples were achieved. A median abundance of 88.10 (Q1=55.01/Q3=114.72) microplastic particles per kg dry sediment or 2862.56 (Q1=1787.34/Q3=3727.28) particles per m2 was found at the beaches on Rügen. Fibers were more abundant than fragments at all beaches. In this study, no statistically significant differences but only tendencies were determined between the beaches with different exposition and anthropogenic activity as well as for distribution patterns which showed that microplastic fragments accumulate in topographic depressions, similar to macrolitter items.

Development of an optimal filter substrate for the identification of small microplastic particles in food by micro-Raman spectroscopy.

When analysing microplastics in food, due to toxicological reasons it is important to achieve clear identification of particles down to a size of at least 1 µm. One reliable, optical analytical technique allowing this is micro-Raman spectroscopy. After isolation of particles via filtration, analysis is typically performed directly on the filter surface. In order to obtain high qualitative Raman spectra, the material of the membrane filters should not show any interference in terms of background and Raman signals during spectrum acquisition. To facilitate the usage of automatic particle detection, membrane filters should also show specific optical properties. In this work, beside eight different, commercially available membrane filters, three newly designed metal-coated polycarbonate membrane filters were tested to fulfil these requirements. We found that aluminium-coated polycarbonate membrane filters had ideal characteristics as a substrate for micro-Raman spectroscopy. Its spectrum shows no or minimal interference with particle spectra, depending on the laser wavelength. Furthermore, automatic particle detection can be applied when analysing the filter surface under dark-field illumination. With this new membrane filter, analytics free of interference of microplastics down to a size of 1 µm becomes possible. Thus, an important size class of these contaminants can now be visualized and spectrally identified. Graphical abstract A newly developed aluminium coated polycarbonate membrane filter enables automatic particle detection and generation of high qualitative Raman spectra allowing identification of small microplastics.

Efficient microplastics extraction from sand. A cost effective methodology based on sodium iodide recycling.

Evaluating the microplastics pollution on the shores requires overcoming the technological and economical challenge of efficient plastic extraction from sand. The recovery of dense microplastics requires the use of NaI solutions, a costly process. The aim of this study is to decrease this cost by recycling the NaI solutions and to determine the impact of NaI storage. For studying the NaI recyclability, the solution density and the salt mass have been monitored during ten life cycles. Density, pH and salt mass have been measured for 40days to assess the storage effect. The results show that NaI solutions are recyclable without any density alterations with a total loss of 35.9% after the 10cycles of use. During storage, chemical reactions may appear but are reversible. Consequently, the use of recycling methods allows for a significant cost reduction. How far the plastic extraction by dense solutions is representative is discussed.

A concept for the removal of microplastics from the marine environment with innovative host-guest relationships.

Environmental pollution caused by inert anthropogenic stressors such as microplastics in aquatic media is constantly increasing. Through the proliferating use of plastic products in daily life, more and more plastic particles enter waters as primary microplastics. Even though large scale plastic items such as plastic bottles and bags represent the highest percentage of plastic waste, their degeneration also generates microparticles and nanoparticles (secondary microplastics). Modern sewage treatment plants require innovative ideas in order to deal with this man-made problem. State-of-the-art technology offers approaches to minimise the amount of microplastics in aquatic systems. These technologies, however, are either insufficient or very costly, as well as time-consuming in both cases. The conceptual idea presented here is to apply innovative inorganic-organic hybrid silica gels which provide a cost-effective and straightforward approach. Currently, the synthesis of preorganised bioinspired compounds is advancing in order to produce functionalised hybrid silica gels in a further step. These gels have the ability to remove stressors such as microplastics from waste water. By means of the sol-gel process, bioinspired silane compounds are currently being permuted to macromolecules and examined with respect to their properties as fixation and filter material in order to remove the hydrophobic anthropogenic stressors sustainably. Here, the reproduction of biological systems plays a significant role. In particular in material sciences, this approach is becoming increasingly important. Among other concepts, new biomimetic molecules form the basis for the investigation of innovative host-guest relationships for anthropogenic stressors in the environment and their implementation in technical processes.