Microplastics and nanoplastics have become emerging particulate anthropogenic pollutants and rapidly turned into a field of growing scientific and public interest. These tiny plastic particles are ...found in the environment all around the globe as well as in drinking water and food, raising concerns about their impacts on the environment and human health. To adequately address these issues, reliable information on the ambient concentrations of microplastics and nanoplastics is needed. However, micro- and nanoplastic particles are extremely complex and diverse in terms of their size, shape, density, polymer type, surface properties, etc. While the particle concentrations in different media can vary by up to 10 orders of magnitude, analysis of such complex samples may resemble searching for a needle in a haystack. This highlights the critical importance of appropriate methods for the chemical identification, quantification, and characterization of microplastics and nanoplastics. The present article reviews advanced methods for the representative mass-based and particle-based analysis of microplastics, with a focus on the sensitivity and lower-size limit for detection. The advantages and limitations of the methods, and their complementarity for the comprehensive characterization of microplastics are discussed. A special attention is paid to the approaches for reliable analysis of nanoplastics. Finally, an outlook for establishing harmonized and standardized methods to analyze these challenging contaminants is presented, and perspectives within and beyond this research field are discussed.
Microplastic in Aquatic Ecosystems Ivleva, Natalia P.; Wiesheu, Alexandra C.; Niessner, Reinhard
Angewandte Chemie International Edition,
February 6, 2017, Letnik:
56, Številka:
7
Journal Article
Recenzirano
The contamination of marine and freshwater ecosystems with plastic, and especially with microplastic (MP), is a global ecological problem of increasing scientific concern. This has stimulated a great ...deal of research on the occurrence of MP, interaction of MP with chemical pollutants, the uptake of MP by aquatic organisms, and the resulting (negative) impact of MP. Herein, we review the major issues of MP in aquatic environments, with the principal aims 1) to characterize the methods applied for MP analysis (including sampling, processing, identification and quantification), indicate the most reliable techniques, and discuss the required further improvements; 2) to estimate the abundance of MP in marine/freshwater ecosystems and clarify the problems that hamper the comparability of such results; and 3) to summarize the existing literature on the uptake of MP by living organisms. Finally, we identify knowledge gaps, suggest possible strategies to assess environmental risks arising from MP, and discuss prospects to minimize MP abundance in aquatic ecosystems.
Something in the water: The contamination of aquatic ecosystems with microplastic (MP) is an ecological problem of increasing concern. Since the MP cannot be effectively removed, the risks it poses must be properly evaluated and strategies developed to minimize environmental damage. This Review summarizes the current state of research in the field and discusses potential strategies for improving the evaluation of MP in aquatic ecosystems and reducing MP pollution.
The accumulation of plastic litter in natural environments is a global issue. Concerns over potential negative impacts on the economy, wildlife, and human health provide strong incentives for ...improving the sustainable use of plastics. Despite the many voices raised on the issue, we lack a consensus on how to define and categorize plastic debris. This is evident for microplastics, where inconsistent size classes are used and where the materials to be included are under debate. While this is inherent in an emerging research field, an ambiguous terminology results in confusion and miscommunication that may compromise progress in research and mitigation measures. Therefore, we need to be explicit on what exactly we consider plastic debris. Thus, we critically discuss the advantages and disadvantages of a unified terminology, propose a definition and categorization framework, and highlight areas of uncertainty. Going beyond size classes, our framework includes physicochemical properties (polymer composition, solid state, solubility) as defining criteria and size, shape, color, and origin as classifiers for categorization. Acknowledging the rapid evolution of our knowledge on plastic pollution, our framework will promote consensus building within the scientific and regulatory community based on a solid scientific foundation.
Plastic waste is of increasing concern in marine ecosystems 1–3. Buoyant plastic particles accumulate in pelagic habitats whereas non-floating debris accumulates on the seafloor and in beach ...sediments, posing risk to the respective communities 1–4. Microplastic particles (<5 mm) are either directly introduced via sewage discharge or formed by biofouling and mechanical abrasion, making them more prone to consumption by aquatic organisms 2,3. As a consequence, they can accumulate in higher trophic levels 3–5. A variety of harmful effects of plastic and associated chemicals has been shown 2–4. Moreover, plastic debris can act as vector for alien species and diseases 2,6. A large portion of the plastic waste is produced onshore and reaches the marine environment, which is considered the main sink of plastic debris. There is, however, a considerable lack of knowledge on the contamination of freshwater ecosystems with plastic debris. We here show that freshwater ecosystems also act, at least temporarily, as a sink for plastic particles.
Nanoplastic is an emerging topic of relevance in environmental science. The analytical methods for microplastic have a particle size limit of a few micrometers so that new methods have to be ...developed to cover the nanometer range. This contribution reviews the progress in environmental nanoplastic analysis and critically evaluates which techniques from nanomaterial analysis may potentially be adapted to close the methodological gap. A roadmap is brought forward for the whole analytical process from sample treatment to particle characterization. This includes a critical review of (i) methods for analyte extraction and preconcentration from various environmental matrices; (ii) methods for the separation of the nanoplastic into specific size fractions; (iii) light scattering techniques and various types of microscopy to characterize the particle fractions; (iv) chemical identification of particles to validate the obtained data. For these methods, we will discuss prospects and limitations to develop analytical protocols for specific sampling scenarios.
•Analytical methods for submicrometer- and nanoplastic face a methodological gap.•Methods for nanomaterial characterization that may be applicable for submicrometer- and nanoplastic are presented.•A roadmap for the whole analytical process of submicrometer- and nanoplastic is discussed.
Biofilms represent the predominant form of microbial life on our planet. These aggregates of microorganisms, which are embedded in a matrix formed by extracellular polymeric substances, may colonize ...nearly all interfaces. Detailed knowledge of microorganisms enclosed in biofilms as well as of the chemical composition, structure, and functions of the complex biofilm matrix and their changes at different stages of the biofilm formation and under various physical and chemical conditions is relevant in different fields. Important research topics include the development and improvement of antibiotics and medical devices and the optimization of biocides, antifouling strategies, and biological wastewater treatment. Raman microspectroscopy is a capable and nondestructive tool that can provide detailed two-dimensional and three-dimensional chemical information about biofilm constituents with the spatial resolution of an optical microscope and without interference from water. However, the sensitivity of Raman microspectroscopy is rather limited, which hampers the applicability of Raman microspectroscopy especially at low biomass concentrations. Fortunately, the resonance Raman effect as well as surface-enhanced Raman scattering can help to overcome this drawback. Furthermore, the combination of Raman microspectroscopy with other microscopic techniques, mass spectrometry techniques, or particularly with stable-isotope techniques can provide comprehensive information on monospecies and multispecies biofilms. Here, an overview of different Raman microspectroscopic techniques, including resonance Raman microspectroscopy and surface-enhanced Raman scattering microspectroscopy, for in situ detection, visualization, identification, and chemical characterization of biofilms is given, and the main feasibilities and limitations of these techniques in biofilm research are presented. Future possibilities of and challenges for Raman microspectroscopy alone and in combination with other analytical techniques for characterization of complex biofilm matrices are discussed in a critical review.
Graphical Abstract
Applicability of Raman microspectroscopy for biofilm analysis
The bio-sensing for the convenient detection of bacteria has been widely explored with the use of various sensing materials and techniques. It is still a challenge to achieve an ultrasensitive and ...selective, but simple, rapid, and inexpensive detection method for bacteria. We report on surface-enhanced Raman scattering (SERS) for the detection of living bacteria in drinking water by employing a synthesis of silver nanoparticles coating the cell wall of bacteria. We found that the Raman signals intensity of bacteria after AgNP synthesis mainly depends on the zeta potential of the cell wall. The enhancement of the Raman signal of bacteria using this strategy is about 30-fold higher than that in the case of a simply mixed colloid–bacterial suspension. The total assay time required is only 10 min and the total reactants’ volume needed to analyze bacteria in a real environment is as low as 1 mL. Particularly, only one droplet of 3 μL sample is necessary for each SERS measurement. Furthermore, we can use this novel strategy to discriminate three strains of Escherichia coli and one strain of Staphylococcus epidermidis by hierarchy cluster analysis. Finally, we can detect bacteria down to 2.5 × 102 cells/mL on a hydrophobic glass slide by SERS mapping. Thus, our detection method offers prominent advantages, such as reduced assay time, simple handling, low reactant volumes, small amount of sample, and higher sensitivity and selectivity compared to previously reported label free methods. This novel strategy may be extended to open an avenue for developing various SERS-based biosensors.
Although plastic debris is constantly accumulating in aquatic environments, the impact on aquatic ecosystems is not yet fully understood. A first important step to assess the consequences of plastic ...debris in aquatic ecosystems is the establishment of a reliable, verified, and standardized method to quantify the amount of plastic particles in the environment. We improved the density separation approach by the construction of the so called Munich Plastic Sediment Separator (MPSS). It enables a reliable separation of different ecologically relevant size classes of plastic particles from sediment samples. A ZnCl2‐solution (1.6–1.7 kg/L) as separation fluid allows for an extraction of plastic particles ranging from large fragments to small microplastic particles (S‐MPP, <1 mm). Subsequent identification and quantification of the particles with spatial resolution down to 1 µm can be performed using Raman microspectroscopy. Our study is the first providing validated recovery rates of 100% for large microplastic particles (L‐MPP, 1–5 mm) and 95.5% for S‐MPP. The recovery rate for S‐MPP, using the MPSS, was significantly higher than the value obtained by application of classical density separation setup (39.8%). Moreover, our recovery rates were significantly higher than those based on froth flotation (55.0% for L‐MPP) commonly used in recycling industries. Hence, our improved method can be used for a reliable and time‐efficient separation, identification and quantification of plastic fragments down to S‐MPP. This will help foster studies quantifying the increasing contamination of aquatic environments with microplastic particles, which is a crucial prerequisite for future risk assessment and management strategies.
Nanoplastic pollution is an emerging environmental concern, but current analytical approaches are facing limitations in this size range. However, the coupling of nanoparticle separation with chemical ...characterization bears potential to close this gap. Here, we realize the hyphenation of particle separation/characterization (field-flow fractionation (FFF), UV, and multiangle light scattering) with subsequent chemical identification by online Raman microspectroscopy (RM). The problem of low Raman scattering was overcome by trapping particles with 2D optical tweezers. This setup enabled RM to identify particles of different materials (polymers and inorganic) in the size range from 200 nm to 5 μm, with concentrations in the order of 1 mg/L (109 particles L–1). The hyphenation was realized for asymmetric flow FFF and centrifugal FFF, which separate particles on the basis of different properties. This technique shows potential for application in nanoplastic analysis, as well as many other fields of nanomaterial characterization.
TUM-ParticleTyper is a novel program for the automated detection, quantification and morphological characterization of fragments, including particles and fibers, in images from optical, fluorescence ...and electron microscopy (SEM). It can be used to automatically select targets for subsequent chemical analysis, e.g., Raman microscopy, or any other single particle identification method. The program was specifically developed and validated for the analysis of microplastic particles on gold coated polycarbonate filters. Our method development was supported by the design of a filter holder that minimizes filter roughness and facilitates enhanced focusing for better images and Raman measurements. The TUM-ParticleTyper software is tunable to the user's specific sample demands and can extract the morphological characteristics of detected objects (coordinates, Feret's diameter min / max, area and shape). Results are saved in csv-format and contours of detected objects are displayed as an overlay on the original image. Additionally, the program can stitch a set of images to create a full image out of several smaller ones. An additional useful feature is the inclusion of a statistical process to calculate the minimum number of particles that must be chemically identified to be representative of all particles localized on the substrate. The program performance was evaluated on genuine microplastic samples. The TUM-ParticleTyper software localizes particles using an adaptive threshold with results comparable to the "gold standard" method (manual localization by an expert) and surpasses the commonly used Otsu thresholding by doubling the rate of true positive localizations. This enables the analysis of a statistically significant number of particles on the filter selected by random sampling, measured via single point approach. This extreme reduction in measurement points was validated by comparison to chemical imaging, applying both procedures to the same area at comparable processing times. The single point approach was both faster and more accurate proving the applicability of the presented program.
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