Determination of Environmental Micro(Nano)Plastics by Matrix-Assisted Laser Desorption/Ionization-Time-of-Flight Mass Spectrometry.

Micro(nano)plastics (MNPs) are widely acknowledged as global environmental threat while determination methods for MNPs are still lacking and becoming a growing concern. This study provides a novel method for MNPs identification/quantification by matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry (MALDI-TOF MS). Factors affecting the measurement were optimized, including laser energy, matrix (M), analyte (A), cationization agent (C), and MAC volume ratio. Under the optimal conditions, the peaks representative of polystyrene (PS) and polyethylene terephthalate (PET) were identified, and the mass differences were consistent with the molecular weight of the corresponding oligomer. A quantitative correlation was built between normalized signal intensity and ln[polymer concentration] with a correlation coefficient above 0.96 for low-molecular-weight polymers and 0.98 for high-molecular-weight polymers. Furthermore, two types of environmental MNP samples were prepared, including aviation cup particles as fresh plastics and aged MNPs extracted from river sediment. By using MALDI-TOF MS, the PS-related MNPs (in both aviation cup and sediment) consisted of C8H8 and C16H16O oligomers, while the PET-related MNPs (only found in sediment) were identified with repeated units of C10H8O4 and C12H12O4. According to the quantitative correlation curve, the contents of PS and PET MNPs were quantified as 8.56 ± 0.04 and 28.71 ± 0.20 mg·kg-1, respectively, in the collected sediment. This study is the first attempt to propose a quantification method with the employment of MALDI-TOF MS for aged MNPs analysis in environmental samples, which can not only supply an effective method for MNP analysis but also inspire future studies on the in situ distribution and transformation of MNPs in environmental and biological samples.

Spatial-temporal distribution of microplastics in surface water and sediments of Maozhou River within Guangdong-Hong Kong-Macao Greater Bay Area.

Concerns over the negative impacts of microplastics on human health have led to growing attention on the occurrence of microplastics in aquatic environment. Recent studies have extended their focus from marine to inland waters, especially on the spatial-temporal distribution of the microplastics in urban rivers. In this study, Maozhou River, the largest river in Shenzhen, a tributary of the Pearl River, was selected as a representative inland waterway of Guangdong-Hong Kong-Macao Greater Bay Area. The spatial-temporal investigation was performed on microplastics in the surface water and sediments of 17 sites along the mainstream of the Maozhou River. Results show that microplastics were widely and unevenly distributed along the river and reached the high abundances on the site most intensively surrounded by industries as well as the sites downstream. The abundances in dry season ranged from 4.0 ± 1.0 to 25.5 ± 3.5 items·L-1 in water and 35 ± 15 to 560 ± 70 item·kg-1 in sediments, which were relatively higher than those observed in the wet season (water: 3.5 ± 1.0 to 10.5 ± 2.5 items·L-1; sediments: 25 ± 5 to 360 ± 90 item·kg-1; p value < 0.05). The dominant types of the microplastics were identified as: PE Polyethylene (PE, water: 45.0%, sediments: 42.0%), polypropylene (PP, water and sediments: 12.5%), polystyrene (PS, water: 34.5%; sediments 14.5%) and polyvinyl chloride (PVC, water: 2.0%; sediments: 15%). Moreover, metals like Al, Si, Ca were discovered on the rough surface of the microplastics, indicating the interactions between the microplastics and the aquatic environment. Through a comprehensive comparison with other major inland waters in China, this work provides valuable data on the microplastics pollution of a representative inland water in the Greater Bay Area, and will further contribute to a better understanding on the land-based input of microplastics from the intensively affected inland waters.

Further understanding on the mechanism of alkyl ketene dimer sizing on the causticized calcium carbonate filled paper and its improvements.

Causticized calcium carbonate (CCC), a solid waste derived from kraft black recovery process, can be used as an alternative for the conventional precipitated calcium carbonate (PCC). However, the application of the CCC has been limited due to its low sizing efficiency in its filled paper. In this study, the characteristics of the CCC were studied aiming to improve the alkyl ketene dimer (AKD) sizing performances of the CCC filled papers, and the results were compared with those from PCC filled papers. The results showed that the CCC had higher pore structure, higher specific surface area, and more negative charge density than the PCC, thus leading to a higher cationic AKD adsorption onto the CCC filler. The lower AKD sizing efficiency in the CCC filled paper can be explained by the combination of higher AKD adsorption and migration, both of which resulted in preferred AKD adsorption onto/into the CCC fillers, rather than the cellulose fibers. Based on the above, the prior addition of polyamide-polyamine epichlorhydrin (PAE) resin to the CCC filler system was proposed to remedy the related issues, thus improving the sizing efficiency.