Portable detection methods for marine micro–nano-plastics

Gang Chenab, Jiahao Donga, Min Daia, Xiaobo Xiongc, Juan Mei*d and Jing Pan*a
aState Key Laboratory of Geomicrobiology and Environmental Changes, Faculty of Materials Science and Chemistry, China University of Geosciences, Wuhan 430074, China. E-mail: panjing@cug.edu.cn
bHubei Sanding Technology Co., Ltd, Ezhou 436000, China
cHubei Key Laboratory of Forensic Science, Hubei University of Police, Wuhan 430034, China
dDepartment of Stomatology, Hunan University of Medicine, Huaihua 418000, China. E-mail: meij@hnmu.edu.cn

Received 29th May 2025 , Accepted 22nd July 2025

First published on 23rd July 2025


Abstract

Every year, millions of tons of plastic waste enter the ocean, gradually breaking into micro–nano-plastics, threatening the ecosystem and human health. The detection of marine micro–nano-plastics is an important link in assessing ecological risks and guiding the implementation of governance. The traditional detection technologies rely on complex equipment and pretreatment, making it difficult to achieve rapid and on-site detection of micro–nano-plastics in seawater environments. Portable detection methods, which can be used for on-site and rapid detection of marine micro–nano-plastics, thus attract more and more attention. Herein, recent existing portable detection methods for marine micro–nano-plastics are introduced. Firstly, the conventional methods of marine micro–nano-plastic sensors and the corresponding advances in portable areas are presented. The conventional methods include pyrolysis gas chromatography-mass spectrometry, infrared spectroscopy and Raman spectroscopy. Then, the novel portable detection methods developed in the recent 5 years for marine micro–nano-plastics are discussed, such as photoluminescence spectroscopy, triboelectric nanogenerator-based self-powered sensors and electrochemical sensors. Finally, the challenges in the development of portable detection methods for marine micro–nano-plastics are demonstrated for practical application.


1 Introduction

According to statistics, millions of tons of plastic waste enter the ocean every year worldwide.1–3 At present, almost all types of plastics can be found in the ocean. Among them, non-degradable resin materials such as polyvinylchloride (PVC), polyamide (PA), polypropylene (PP), polystyrene (PS), polyethylene (PE), and poly(methyl methacrylate) (PMMA) are the main ones.4–6 Under the influence of ultraviolet rays, ocean turbulence, planktons and other factors, these plastics decompose into invisible micro–nanoparticles.7–9 Plastic particles with a size ranging from 1 to 5000 μm are generally referred to as microplastics, and those smaller than 1 μm are called nanoplastics.10–12 Studies show that the toxicity of microplastics and nanoplastics to living organisms is inversely proportional to the size and shape of the particles.13,14 The smaller the size, the greater the toxicity may be.15–19 For instance, no microplastics were found in the exposed fish brains, but nanoplastics were observed to cross the blood–brain barrier and accumulate in the fish brains, leading to behavioral disorders and oxidative DNA damage.20,21 Some of these micro–nano-plastics are transferred to the human body through the food chain (Fig. 1).22–25 Researchers have found traces of micro–nano-plastic particles in human placentas, feces, blood, breast milk, as well as organs and tissues such as the liver and lungs.26,27 These particles can accumulate silently in the human body and transfer along with the life activities of the human body, causing cytotoxic reactions such as oxidative stress and inflammation,28 threatening human health.19,29
image file: d5an00597c-f1.tif
Fig. 1 The source and hazards of marine micro–nano-plastics30 (reprinted with permission from ref. 30. Copyright 2019 American Chemical Society).

In 2016, the United Nations Environment Assembly identified marine plastic debris and micro–nano-plastics as major global environmental issues.31 In recent years, scientists have begun research and governance work on the distribution, migration, toxicology and management of marine micro–nano-plastics.32–34 The further development of these works still requires reliable data on the distribution of micro–nano-plastics in the marine environment and the composition of the involved polymers as support.35–37 Therefore, developing detection methods for micro–nano-plastics in the ocean is particularly important.38–40 It not only concerns the health and sustainable development of marine ecosystems but is also a key link in achieving the national plastic pollution control goals.41–44

However, the commonly used detection methods for micro–nano-plastics mostly rely on complex equipment and all require complex sample pretreatment processes.45 When testing seawater samples, samples can only be taken first and then brought back to the laboratory for processing and testing. Not only does it take a long time from sampling to the completion of the test, but also the processes of sample collection, transportation, storage and processing increase the difficulty of the test and the probability of sample contamination. Due to the shortcomings of the commonly used detection methods at present, the relevant data on marine micro–nano-plastic pollution are very limited at present, which hinders further in-depth research on it.46,47 Therefore, there is an urgent need to develop portable detection technology for marine micro–nano-plastics to reduce operational complexity, improve detection timeliness, and enable research on marine micro–nano-plastic pollution to obtain spatial coverage, sampling frequency and time series data that cannot be achieved by current technologies, thereby promoting the rapid development of this field.

Actually, various excellent reviews have discussed the advances and limitations in portable plastic detection.48–51 However, for practical use, the problems faced in different detection environments are different. For example, marine plastic detection faces a more complex environment than the plastics in other environments. The more interfering substances and factors make the marine plastics more difficult to analyze. In light of the great importance and increasing attention on marine pollution, specifically reviewing the advances in the aspect of marine micro–nano-plastics is becoming highly necessary. In addition, many novel detection methods have been developed for marine micro–nano-plastics and they have never been summarized before. The existing related reviews still focus on mass spectrometry and spectroscopic instruments. Herein, recent existing portable detection methods for marine micro–nano-plastics are demonstrated (Fig. 2), including not only the conventional methods of pyrolysis gas chromatography-mass spectrometry, infrared spectroscopy and Raman spectroscopy, but also the novel detection methods, such as photoluminescence spectroscopy, triboelectric nanogenerator-based self-powered sensors and electrochemical sensors. In addition, the challenges in the development of portable detection methods for marine micro–nano-plastics are analyzed for practical application. This specific review is prepared with the hope that it could arouse more attention on the efficient and low-cost marine plastic pollution monitoring technologies and offer valuable insight into plastic pollution control.


image file: d5an00597c-f2.tif
Fig. 2 The main content of this review.

2 Traditional detection methods and the corresponding advances

2.1 Pyrolysis gas chromatography-mass spectrometry (PYR-GC/MS)

Compared with plastics in other environments, the environment of marine plastics is more complex, with more interfering substances and factors, making it more difficult to detect them.52 Anna P. M. Michel and her research group studied the accuracy rates of detection of consumer plastics and detection of marine plastics, employing the combination of different commonly used rapid detection methods with machine learning.53 For detection of consumer plastics, the success rates of near-infrared reflectance spectroscopy, laser-induced breakdown spectroscopy, and X-ray fluorescence spectroscopy are 91%, 97%, and 70%, respectively. However, for the detection of marine plastics, the success rates are decreased to 81%, 76%, and 66%.

The commonly used detection techniques for marine micro–nano-plastics are shown in Fig. 3. Among them, the most widely used one is the detection method based on PYR-GC/MS.54 This method mainly combines thermal cracking technology and gas chromatography-mass spectrometry (GC-MS) technology. The sample is rapidly heated and cracked under an inert atmosphere, and the cracking products are placed in a gas chromatography device for separation. Finally, the separated cracking products are detected by mass spectrometry and the composition of the original sample is analyzed.56,57 Previously, the data processing methods were time-consuming.58,59 However, later on, automated algorithms emerged, which shortened the time for data analysis and also provided a standardized process for data processing in plastic mixtures. For instance, Kazuko Matsui et al. developed an algorithm for the composition identification of polymer mixtures and successfully identified four types of marine polymers.59


image file: d5an00597c-f3.tif
Fig. 3 (a) Advantages and disadvantages of PYR-GC/MS54 (reprinted with permission from ref. 54. Copyright 2021 American Chemical Society). (b) Advantages and disadvantages of Raman spectroscopy30 (reprinted with permission from ref. 30. Copyright 2019 American Chemical Society). (c) Advantages and disadvantages of infrared spectroscopy55 (reprinted with permission from ref. 55. Copyright 2018 American Chemical Society).

This method has good detection specificity and sensitivity. However, a series of pretreatments are required before detection to achieve the enrichment of trace micro–nano-plastics in seawater, and the detection process is complex. For portable applications, the size of the PYR-GC/MS system should be much decreased and the complex separation/extraction processes should be avoided. To achieve this goal, Jie Jiang et al. designed a pyrolyzer and combined it with a portable mass spectrometer (Fig. 4a and b).60 The size of the miniaturized PYR-GC/MS system reached as small as 70 cm (L) × 30 cm (W) × 40 cm (H) and the weight is only 18 kg. The power is supplied by a 180 W internal battery. Additionally, micro-particles can be decomposed in the designed pyrolyzer followed by analysis using the portable mass spectrometer. The complex separation/extraction processes can be avoided and rapid analysis in 5 min can be achieved. The detection accuracy (Fig. 4c and d) of this portable pyrolysis-mass spectrometer was confirmed based on four common plastics (PE, PP, PS, and PMMA). The practical potential was also verified based on authentic samples from a beach.


image file: d5an00597c-f4.tif
Fig. 4 (a) The schematic and (b) photograph of portable pyrolysis-mass spectrometry. (c) The detection results for PE, PP, (d) PS, and PMMA60 (reprinted with permission from ref. 60. Copyright 2020 American Chemical Society).

2.2 Spectroscopic instruments

Due to their rapid detection processes and the excellent detection specificity brought by the characteristic spectra of plastics, spectroscopic technologies provide the possibility for the realization of the detection of marine micro–nano-plastics.61–64 Typical examples include infrared spectroscopy (IR) and Raman spectroscopy,65–67 which are also frequently used for the detection of marine micro–nano-plastics and have given rise to a series of combined or optimized detection methods, such as Raman tweezers technology,30 Raman and IR combined detection55 and so on. In recent years, portable and miniaturized IR devices and Raman spectrometers have also achieved great progress.68

The basic principle of plastic detection using IR devices is that plastics can selectively absorb specific wavelengths of infrared rays, thereby triggering the energy level transitions of their molecular vibrations and rotations. By analyzing the infrared spectrum of the plastic, its molecular structure, chemical composition, and content can be obtained. The existing marine plastics targeting portable and miniaturized IR devices include short-wave infrared cameras69 or imagers,70 thermal infrared cameras,71,72 hyperspectral imaging devices,73 near-infrared spectroscopy (NIR) devices, and so on. Many portable or miniaturized infrared devices have even been commercially applied, especially NIR devices, on account of their faster analysis process,74 non-destructive detection ability and simultaneous multiple component detection capacity.75,76 The first handheld NIR spectrometer (microPHAZIR, Fig. 5a), which adopted a single-pixel InGaAs detector, a low-power tungsten bulb source and a programmable Hadamard mask, was officially publicized in 2006.68,77 This instrument possesses rapid scanning ability and can record a full spectrum in 10 s with an optical resolution of 11 nm and a good S/N level. The on-site detection capacity was endowed by a Li-ion battery power source and a simple operating system with a display screen and a user interface. Nevertheless, its narrow-wavelength region (1596–2396 nm, 6267–4173 cm−1) imposes limitations on its practical application. Thus, many other portable or miniaturized IR devices have been developed, such as the DLP NIRscan Nano evaluation module (Fig. 5b),78,79 NeoSpectra (Fig. 5c),80 nanoFTIR NIR (Fig. 5d),81 NIRONE Sensor S (Fig. 5e),82 and MicroNIR Pro ES 1700 (Fig. 5f).68


image file: d5an00597c-f5.tif
Fig. 5 Typical commercial miniaturized NIR spectrometers. (a) microPHAZIR, (b) DLP NIRscan Nano evaluation module, (c) NeoSpectra, (d) nanoFTIR NIR, (e) NIRONE Sensor S, and (f) MicroNIR Pro ES 170068 (reprinted with permission from ref. 68. Copyright 2021 Wiley).

Raman spectroscopy analyzes the chemical and structural information of materials by utilizing scattered light and is used for identifying plastics. Compared to IR, Raman spectroscopy can avoid the interference of water molecules and thus is more suitable for the analysis of micro–nano-plastics in seawater.83 To overcome the drawback of traditional Raman spectrometers being nonportable, many lightweight, miniature, and rapid instruments have also been developed.84 The size of the Raman spectrometers can be much decreased to be handheld or even fit into the palm. However, considering the small sizes, the screens of the handheld or palm instruments are also very small, which cannot present the complete spectrum. Therefore, the software, which can automatically offer the matching result between the spectrum and the database, is usually equipped for these kinds of devices. This phenomenon makes it difficult for these kinds of instruments to accurately identify individual target substances in mixture samples or complex authentic samples, for example, seawater. Thus, classification algorithms have been introduced to in situ analyze microplastics in complex authentic samples and have obtained enhanced detection accuracy and efficiency.85

Other than classification algorithms, a variety of new technologies have been introduced to Raman spectroscopy techniques to improve their practicability for the detection of marine plastics. For example, Tomoko Takahashi et al. combined Raman spectroscopy with digital holography and realized in situ continuous marine plastics’ monitoring (Fig. 6).86 The detection can even be executed in the deep sea (water depth of 900 m) with extremely low plastic density. Technically speaking, the detection was performed by a collimated continuous wave laser beam for the simultaneous acquisition of the Raman spectrum and hologram. From the hologram, the shape and size of the plastics can be figured out. From the Raman spectrum, the composition of the plastics can be analyzed.


image file: d5an00597c-f6.tif
Fig. 6 (a) The photograph, (b) the obtained holographic image, and (c) the obtained Raman spectrum of the in situ Raman device, which combined Raman spectroscopy and digital holography86 (reprinted with permission from ref. 86. Copyright 2019 IEEE). (d) The structure, (e) the result image with 1 ms pixel dwell time, and (f) the result image with 2 ms pixel dwell time of the compressive Raman spectroscopy system87 (reprinted with permission from ref. 87. Copyright 2024 Elsevier).

Besides, for portable uses, Raman analysis would be best to offer a spatially resolved map for on-site analysis of marine plastics and the detection time should be as short as possible. However, in practical cases, more than 10 milliseconds are usually needed to integrate a viable Raman signal, resulting in a long time (up to tens of hours) for the acquisition of all the Raman signals for one detection and difficulty in obtaining a spatially resolved Raman map.88–90 To overcome this problem, Hervé Rigneault et al. combined single-pixel detection with binary spectral filters and developed a compressive Raman technology.87 This technology can image rapidly as well as classify 6 kinds of marine micro-plastics in an area of 1 mm2 within 2 hours. The spatial resolution is 1 μm. This speed is 10–100 times faster than existing studies.

Although these combined or optimized detection methods can further optimize the detection results, they cannot avoid the limitations brought by the detection principles of Raman spectroscopy and infrared spectroscopy. For instance, in Raman detection, biological residues in seawater samples can cause a fluorescence background to be generated during Raman detection, significantly reducing the spectral quality and even making detection impossible.91 Therefore, the detection methods based on Raman spectroscopy usually need to purify the sample before detection to prevent the generation of fluorescence. On the other hand, the sample of IR must be dried before measurement, in view of the strong infrared radiation absorption of water. In addition, the environment of the ocean can obviously alter the properties of plastics and change the spectrum, leading to inaccurate test results.92 These factors all limit the application of Raman and infrared spectroscopy techniques for on-site rapid detection of marine micro–nano-plastics.93

3 Novel detection methods

3.1 Photoluminescence spectroscopy

Spectroscopic technology is one of the most mature technologies to realize the detection of marine micro–nano-plastics.31 However, as mentioned above, the portable analysis for marine micro–nano-plastics is difficult to accomplish using FTIR/Raman spectrometers, ascribed to the organic interfering substances and water environment.94 Pretreatment steps are needed for marine samples, including the separation of micro–nano-plastics from the matrix, the removal of water and so on. These pretreatment steps are obviously not conducive to portable detection.51

One promising resolution is based on the photoluminescence of plastics. For example, Ornik et al. employed a blue light (405 nm)-emitting laser diode to obtain the luminescence spectra of natural marine samples and bulk plastic samples.95 The different photoluminescence spectra of plastic and non-plastic materials offer a possibility of eliminating the disturbance of organic interferents through optical methods. In addition, the interference by organic materials can be further excluded based on sophisticated chemometrics. In fact, the autofluorescence of plastics has already been employed to detect micro–nano-plastics in various real samples in different places.96–98

Although the autofluorescence signals of plastics can be directly used to identify micro–nano-plastics in real samples, the weak intensity leads to insufficient detection sensitivity and specificity.99 Therefore, they are often used for qualitative detection rather than quantitative detection. For quantitative detection, dyes are commonly introduced in most of the related research. Considering the mature staining protocols as well as explicit absorption and emission spectra, commercial fluorophores have been widely used as dyes for the specific and quantitative detection of micro–nano-plastics in environmental matrices. Among all the commercial fluorophores used for the detection of micro–nano-plastics, the most extensively adopted one is Nile Red (9-diethylamino-5H-benzo[α]phenoxazine-5-one). Nile Red is a kind of hydrophobic fluorophore and emits strong fluorescence only in a hydrophobic environment. In the analysis of plastic particles, Nile Red exhibits an advantageous characteristic, solvatochromism. Solvatochromism means that the fluorescence emission spectrum can redshift obviously when the medium's polarity increases. The reason lies in the dye molecule's twisted intramolecular charge transfer state.100 Solvatochromism endows Nile Red with the ability to classify plastics based on their general hydrophobicity.101

However, for the detection of marine micro–nano-plastics, the hydrophobicity of plastics could be affected by other substances in the sea water, resulting in a changed emitted colour of Nile Red and inaccurate test results.103 Besides, Nile Red can not only dye plastics but also other organic substances, leading to false positive results or a higher test result than the true plastic content. Although purification and pretreatment can remove organic substances from samples, they go against portable detection.104 Therefore, Thomas Stanton and his group adopted the other method and additionally employed a second dye (4′,6-diamidino-2-phenylindole, DAPI) to stain biological materials. Under a fluorescence microscope, green fluorescence and blue fluorescence (Fig. 7) were observed for Nile Red (excitation wavelength: 430–490 nm; emission wavelength: 510–560 nm) and DAPI (excitation wavelength: 355–405 nm; emission wavelength: 420–480 nm), respectively.102 Based on the blue fluorescence, the false positive results (the biological materials) under Nile Red staining conditions can be figured out. In this way, the overestimations of microplastic abundance in freshwater samples (10.8%) and in drinking water (100%) were estimated.


image file: d5an00597c-f7.tif
Fig. 7 Fluorescence from Nile Red and DAPI-stained samples102 (reprinted with permission from ref. 102. Copyright 2019 American Chemical Society).

Other than commercial fluorophores, other novel dyes or labeling strategies have been developed recently. For instance, Tianxi Yang and his group members used a supramolecular labeling strategy and utilized luminescent metal-phenolic networks to efficiently label micro–nano-plastics based on their sizes (e.g., 50 nm–10 μm).105 The matching wireless portable device (Fig. 8) can realize sensitive, rapid, and on-site monitoring of micro–nano-plastics. Additionally, quantitative fluorescence imaging can be acquired by machine learning algorithms and remote data processing. The entire detection process is user-friendly and can be operated by untrained personnel to carry out remote data processing on the corresponding APP. In consequence, 330 microplastics and 3.08 × 106 nanoplastics can be quantified in less than 20 min. The test results also support the possibility of real sample testing, for example, a tap water sample. Considering the low-cost analysis ($0.015 per assay), quantitative imaging, and customized data processing, this analytical platform exhibits potential for portable marine micro–nano-plastic detection.


image file: d5an00597c-f8.tif
Fig. 8 The schematic diagram of the detection process of the wireless portable device based on fluorescence imaging105 (reprinted with permission from ref. 105. Copyright 2024 American Chemical Society).

3.2 TENG-based detection methods

In recent years, self-powered sensors based on triboelectric nanogenerators (TENGs) have received extensive attention in outdoor scenarios because they greatly simplify the device structure and are conducive to miniaturization.106–110 Based on the triboelectric effects, different materials can be recognized and distinguished.111–115 The working principle of triboelectric nanogenerators is mainly based on the contact electrification effect and the electrostatic induction effect.116–119 When a liquid comes into contact with a solid, a double electric layer at the liquid–solid interface is formed. The positive charges in the liquid phase will disrupt the original charge balance between the copper electrode and the negatively charged friction material on its surface, causing electrons to flow from the ground wire to the copper electrode to neutralize the positive charges inside it, thereby generating a current in the external circuit. When the liquid slides away, the charge balance at the liquid–solid interface is disrupted, causing electrons to flow out from the copper electrode and resulting in the generation of a reverse current. The periodic contact and separation between liquids and solids can lead to the generation of regular output electrical signals.120

Based on the above principles, when using an active self-powered sensor to detect the analyte, after the friction material surface adsorbs the analyte in the liquid sample, its surface chemical composition and the ability to gain and lose electrons will change. This change further affects the ability of the triboelectric nanogenerator to convert the mechanical energy of the flowing liquid sample into electrical energy, resulting in a corresponding change in the intensity of the output electrical signal and achieving detection. Therefore, theoretically speaking, when detecting micro–nano-plastics in seawater, different kinds and contents of micro–nano-plastics will have different effects on the triboelectric generation process and bring different output signals. In this way, quantitative and specific detection of micro–nano-plastics can be achieved.

However, in actual detection, since the output signal is only an electrical signal, it is difficult to distinguish whether the signal change comes from different kinds or contents of micro–nano-plastics or the charged interfering substances in seawater. Ultimately, it leads to the dilemma in using TENG-based portable detection devices to conduct quantitative and specific detection of micro–nano-plastics in seawater. At present, relevant scientific researchers have begun to try various methods to solve this difficult problem. For instance, Aimiao Qin et al. have introduced a deep learning model to a liquid–solid triboelectric nanogenerator.121 The minimum detection limits of PE, PP, PVC, PET, and PS microplastic particles are 0.0068, 0.0194, 0.0162, 0.0223, and 0.0222 wt%,122 respectively (Fig. 9a). After the training and test by the convolutional neural network depth learning model (Fig. 9b), the high recognition accuracy can be achieved. The average recognition accuracy of the five microplastic particles can reach 86.7% and the recognition accuracy of PS can be as high as 100% (Fig. 9c).


image file: d5an00597c-f9.tif
Fig. 9 (a) The output electrical properties of the TENG-based microplastic sensor for different microplastic contents and types. (b) The operation training chart of the convolutional neural network depth learning model. (c) The obtained confusion matrix after the deep learning121 (reprinted with permission from ref. 121. Copyright 2023 American Chemical Society).

The TENG technology can also work with other technologies to realize portable, rapid and in situ micro-particle detection in liquid samples. For instance, Mina Hoorfar et al. combined microfluidics technology and TENG technology to develop a miniaturized microplastic sensor (Fig. 10). The counting and size analysis were achieved by the similar value of the microfluidic devices’ length scale and microplastic particles’ size (from sub-micron to millimetres). Employing this triboelectric microfluidic sensor, the quantity of PS microspheres with diameters in the range of 0.5 to 10 mm can be detected.123


image file: d5an00597c-f10.tif
Fig. 10 The schematic diagram of the microfluidic chip used for a triboelectric microfluidic micro-particle sensor123 (reprinted with permission from ref. 123. Copyright 2023 the Royal Society of Chemistry).

Compared with the existing detection methods for micro–nano-plastics in the ocean, the TENG-based detection technology features a simple and rapid detection process and a portable device structure.124–127 It can shorten the detection time, enhance the timeliness of data, reduce the detection cost, improve the detection efficiency and flexibly respond to complex marine environments.116,128–132 This can assist researchers in studying the distribution, migration and transformation processes of marine micro–nano-plastics in the marine environment and also enable laboratory personnel to complete monitoring tasks more efficiently and respond to sudden environmental incidents in a timely manner. Therefore, the active self-powered sensor based on triboelectric nanogenerators has great potential to achieve on-site rapid detection of micro–nano-plastics in seawater and become a powerful tool for the research and supervision of marine micro–nano-plastics.133

3.3 Electrochemical methods

Electrochemical methods, which are of low cost, with a fast detection process, and can be integrated with micro-devices, are theoretically very appropriate for the portable detection of marine micro–nano-plastics.134,135 The detection by electrochemical methods is accomplished by the interaction of the analytes and the sensing interface.136–140 The sensing interface can be the surface of the electrode or the binding site of the functional materials modified on the surface of the electrode.141–145 The electrode materials involved in the electrochemical detection of micro–nano-plastics include a glassy carbon electrode,146 graphene,147 biochar materials,148 carbon nanohorns,149 Pt,150 Au,151 MgO nanosheets,152 and so on. However, single materials usually exhibit unsatisfactory detection performance. Composite materials can combine the advantages of each material and further enhance the detection performance. For example, Chérif Dridi et al. fabricated a bisphenol A electrochemical sensor employing a composite of Au nanoparticles and carbon black (Fig. 11a–c).153,154 These constituents of the composite material ensure high electronic conductivity of the electrode. In consequence, a detection concentration in the range of 0.5–15 μM with a limit of detection of 60 nm can be obtained.
image file: d5an00597c-f11.tif
Fig. 11 (a) The mechanism of BPA oxidation reaction. (b) Electrochemical detection result and (c) analysis of the corresponding sensor for bisphenol A in PBS (0.1 M, pH 7.0)153 (reprinted with permission from ref. 153. Copyright 2021 Elsevier). (d) The selectivity of the β-mercaptoethylamine-modified Au electrode. (e) The detection performance towards mixed nanoparticles with different sizes. (f) The distribution of average sizes based on the nonlinear correlation between the current and PS size155 (reprinted with permission from ref. 155. Copyright 2024 American Chemical Society).

Besides electrode materials, functional molecules have been employed to realize the high performance detection of micro–nano-plastics. For instance, Minghui Yang and his group members adopted positively charged β-mercaptoethylamine as the functional molecule and modified it on the surface of an Au electrode to construct a sensing interface (Fig. 11d–f).155 Considering that most PS micro–nano structures are negatively charged, the positively charged β-mercaptoethylamine can capture them by electrostatic interaction. On the other side, ferrocene molecules, which worked as electrochemical beacons, can be modified on the surface of PS micro/nano-structures by hydrophobic interactions. In this way, the DPV electrochemical method can be employed to detect PS micro/nano-structures. This functional molecule-based sensor shows a nonlinear relationship between the current response and the PS size. However, it can only provide average particle sizes instead of the exact size of each PS particle for mixed samples. In addition, it can only achieve precise size analysis in concentration-known samples. Although it has these disadvantages, the miniature structure of the electrode still makes it have potential in the portable detection of marine micro/nano-plastics.

The electrochemical method can also be combined with other detection methods to build a dual-mode sensor. In contrast to the traditional single-mode, the dual-mode form can offer a self-checking function and avoid the false positive results of single mode by cross-validation of the two modes, thus enhancing the detection accuracy.157,158 The key to electrochemical-photoelectrochemical dual-mode sensors lies in the heterojunction formed by two semiconductors. For instance, Ye Zhang et al. employed a CdS/CeO2 heterojunction to fabricate an electrochemical-photoelectrochemical dual-mode portable sensor for the rapid detection of PS nanostructures (Fig. 12).156 The obtained data can be seamlessly transferred to a smartphone and real-time monitoring can be achieved. The obtained detection linear range and detection limit are 0.5–800 μg mL−1 and 0.38 ng mL−1, respectively. For real water detection, the relative standard deviation for the inter-day precision ranges from 0.4% to 2.97% and the value is in the range of 0.94%–4.65% for the intra-day condition. However, the current TENG-based detection methods and electrochemical methods still have relatively low specificity and sensitivity. Moreover, it is difficult to analyze the size and shape of plastics using these methods. Therefore, there is still a considerable distance to go before they can be practically applied.


image file: d5an00597c-f12.tif
Fig. 12 (a) Schematic diagram of electrochemical–photoelectrochemical dual-mode portable sensors. (b) The photoelectrochemical detection results and (c) electrochemical results for NP nanostructures in the concentration range of 0.5–800 μg mL−1 (ref. 156) (reprinted with permission from ref. 156. Copyright 2024 Elsevier).

4 Summary and challenges

In conclusion, the portable detection methods for marine micro–nano-plastics are summarized. The most widely employed traditional detection methods for micro–nano-plastics include pyrolysis gas chromatography-mass spectrometry, infrared spectroscopy and Raman spectroscopy. The corresponding portable devices have also been developed and some of them have even realized commercial use. However, according to the detection mechanism of these methods, most of them need sample pretreatment or result in high false positive results, limiting their practical application. Recently, various novel portable detection methods or mechanisms have been developed for marine micro–nano-plastics, such as photoluminescence spectroscopy, TENG-based self-powered sensors, and electrochemical methods.

Although great advances have been achieved in the detection of portable marine micro–nano-plastics, some challenges are still present. (1) At present, most portable devices can only achieve rapid and quantitative detection of target molecules in simple samples containing a single target. However, seawater contains high concentrations of salt ions and various interfering substances, resulting in insufficient specificity and sensitivity of these devices. In addition, after plastics enter the ocean, a series of changes occur, which interfere with the test results. Therefore, a time-dimensional analysis of marine micro–nano-plastics is also needed. (2) The current portable detection methods find it difficult to simultaneously determine the concentration, size and morphology of marine micro–nano-plastics in the samples. Therefore, more detailed distinction and analysis of the detection signals are still required. (3) The results obtained by different detection methods vary and cannot be directly compared. Therefore, there is still a lack of a measurement standard. We hope this review will provide new ideas for the development of efficient and low-cost marine plastic pollution monitoring technologies and contribute to plastic pollution control.

Author contributions

G. C. wrote the original draft. J. H. D., M. D., and X. B. X. helped to prepare the images and revise the format. J. P. and J. M. guided the structure and finalized the manuscript. All authors contributed to the general discussion.

Conflicts of interest

There are no conflicts to declare.

Data availability

No new data were generated during this study. All analyzed datasets are publicly available and cited appropriately.

Acknowledgements

This work was supported by the National Natural Science Foundation of China (22204150), Noncommunicable Chronic Diseases-National Science and Technology Major Project (2024ZD0531600) as well as the Natural Science Foundation of Hubei Province of China (2021CFB321).

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