Unraveling the Marine Microplastic Cycle: The First Simultaneous Data Set for Air, Sea Surface Microlayer, and Underlying Water.

Microplastics (MP) including tire wear particles (TWP) are ubiquitous. However, their mass loads, transport, and vertical behavior in water bodies and overlying air are never studied simultaneously before. Particularly, the sea surface microlayer (SML), a ubiquitous, predominantly organic, and gelatinous film (<1 mm), is interesting since it may favor MP enrichment. In this study, a remote-controlled research catamaran simultaneously sampled air, SML, and underlying water (ULW) in Swedish fjords of variable anthropogenic impacts (urban, industrial, and rural) to fill these knowledge gaps in the marine-atmospheric MP cycle. Polymer clusters and TWP were identified and quantified with pyrolysis-gas chromatography-mass spectrometry. Air samples contained clusters of polyethylene terephthalate, polycarbonate, and polystyrene (max 50 ng MP m-3). In water samples (max. 10.8 µg MP L-1), mainly TWP and clusters of poly(methyl methacrylate) and polyethylene terephthalate occurred. Here, TWP prevailed in the SML, while the poly(methyl methacrylate) cluster dominated the ULW. However, no general MP enrichment was observed in the SML. Elevated anthropogenic influences in urban and industrial compared to the rural fjord areas were reflected by enhanced MP levels in these areas. Vertical MP movement behavior and distribution were not only linked to polymer characteristics but also to polymer sources and environmental conditions.

Determination of polyurethanes within microplastics in complex environmental samples by analytical pyrolysis.

Polyurethanes (PUR) are a group of polymers synthesized from different diisocyanate and polyol monomers resulting in a countless number of possible structures. However, the large market demand, and the variety of application fields justify the inclusion of PUR in microplastic (MP) investigation. This study aimed at providing comprehensive information on PUR within MP analysis by pyrolysis-gas chromatography-mass spectrometry to clarify whether (i) it is possible to make a reliable statement on the PUR content of environmental samples based on a few pyrolysis products and (ii) which restrictions are required in this context. PUR were managed as subclasses defined by the diisocyanates employed for polymer synthesis. Methylene diphenyl diisocyanate (MDI)- and toluene diisocyanate (TDI)-based PUR were selected as subclasses of greatest relevance. Different PUR were pyrolyzed directly and under thermochemolytic conditions with tetramethylammonium hydroxide (TMAH). Distinct pyrolytic indicators were identified. The study supported that the use of TMAH greatly reduced the interactions of pyrolytic MP analytes with the remaining organic matrix of environmental samples and the associated negative effects on analytical results. Improvements of chromatographic behavior of PUR was evidenced. Regressions (1-20 µg) showed good correlations and parallelism tests underlined that quantitation behavior of different MDI-PUR could be represented by the calibration of just one representative with sufficient accuracy, entailing a good estimation of the entire subclass if thermochemolysis were used. The method was exemplary applied to road dusts and spider webs sampled around a plastic processing plant to evaluate the environmental spread of PUR in an urban context. The environmental occurrence of MDI-PUR as MP was highly influenced by the proximity to a potential source, while TDI markers were not observed.

Hitchhiking into the Deep: How Microplastic Particles are Exported through the Biological Carbon Pump in the North Atlantic Ocean.

Understanding residence times of plastic in the ocean is a major knowledge gap in plastic pollution studies. Observations report a large mismatch between plastic load estimates from worldwide production and disposal and actual plastics floating at the sea surface. Surveys of the water column, from the surface to the deep sea, are rare. Most recent work, therefore, addressed the "missing plastic" question using modeling or laboratory approaches proposing biofouling and degradation as the main removal processes in the ocean. Through organic matrices, plastic can affect the biogeochemical and microbial cycling of carbon and nutrients. For the first time, we provide in situ measured vertical fluxes of microplastics deploying drifting sediment traps in the North Atlantic Gyre from 50 m down to 600 m depth, showing that through biogenic polymers plastic can be embedded into rapidly sinking particles also known as marine snow. We furthermore show that the carbon contained in plastic can represent up to 3.8% of the total downward flux of particulate organic carbon. Our results shed light on important pathways regulating the transport of microplastics in marine systems and on potential interactions with the marine carbon cycle, suggesting microplastic removal through the "biological plastic pump".

Occurrence and backtracking of microplastic mass loads including tire wear particles in northern Atlantic air.

Few studies report the occurrence of microplastics (MP), including tire wear particles (TWP) in the marine atmosphere, and little data is available regarding their size or sources. Here we present active air sampling devices (low- and high-volume samplers) for the evaluation of composition and MP mass loads in the marine atmosphere. Air was sampled during a research cruise along the Norwegian coast up to Bear Island. Samples were analyzed with pyrolysis-gas chromatography-mass spectrometry, generating a mass-based data set for MP in the marine atmosphere. Here we show the ubiquity of MP, even in remote Arctic areas with concentrations up to 37.5 ng m-3. Cluster of polyethylene terephthalate (max. 1.5 ng m-3) were universally present. TWP (max. 35 ng m-3) and cluster of polystyrene, polypropylene, and polyurethane (max. 1.1 ng m-3) were also detected. Atmospheric transport and dispersion models, suggested the introduction of MP into the marine atmosphere equally from sea- and land-based emissions, transforming the ocean from a sink into a source for MP.

Plastic in the air?! - Spider webs as spatial and temporal mirror for microplastics including tire wear particles in urban air.

Studies concerning quantities of microplastics (MP) including tire wear particles (TWP) contamination in air samples are scarce. Spider webs have been suggested as a cheap and easily accessible biomonitor particularly for inorganic contaminates. Here, we emphasize the potential of spider webs to gain insights in the spatial and temporal trends of MP in urban air. The samples, collected in a mid-sized German city, were processed with Fentons reagent and measured using pyrolysis-gas chromatography-mass spectrometry for specific, polymer related indicator compounds. All samples contained TWP and other MP. The latter are detected and quantified as pyrolysis products of a polymer backbone. The results were expressed as clusters (prefix "C"). Determined polymer contaminations ranged from 11.4 µg/mg to 108 µg/mg spider web sample. The dominant polymer was C-PET (Ø 36.0% of total MP) derived most likely from textile fibers. Additionally, there was evidence for traffic-related contaminations. In particular car tire tread (Ø 40.8% of total MP) and ⁎C-PVC (Ø 12.0% of total MP) were found, with the latter presumably originating from paint used for road markings. Truck tire tread, C-PE, C-PP, C-PS, C-PMMA, and C-PC were also frequently found, but in much lower abundance (Ø <6.4% of total MP). Differences in contamination levels could be plausibly related to the sampling locations.

Car and truck tire wear particles in complex environmental samples - A quantitative comparison with "traditional" microplastic polymer mass loads.

Tire wear particles (TWP) are assumed to be the most dominant source of environmental microplastics (MP). Besides rubber components around 60% of tires are additives such as filling material and various chemicals added for vulcanization. The inevitably released TWP in daily traffic are therefore considered a threat to the ecosystem. Nevertheless, published studies on MP mass loads often exclude elastomers. Data concerning composition and concentrations of TWP compared to prominent "traditional" MP polymers, such as polyethylene, polypropylene, poly(ethylene terephthalate) and poly(vinyl chloride), are missing. Identification and quantification of TWP was implemented in an existing pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) method for MP determination. An approach to differentiate between car and truck tire wear and to quantify their respective mass loads is presented. Complex environmental samples such as road dust, fresh water and marine sediments, blue mussels, and marine salts were partly retrospectively analyzed using Py-GC/MS. The results showed ratios of car to truck tire wear up to 16 to 1 and underline the dominance of car compared to truck tire wear mass loads in all analyzed samples. Even though some retrospective data sets might be affected by suboptimal density separation conditions (NaBr, ρ = 1.5 g/cm3), TWP concentrations in road dust clearly exceeded those of "traditional" MP (Ø 5 g TWP vs 0.3 g MP per kg road dust (dry weight). Samples included in this study, which were archived further away from TWP sources such as roads, reflected decreasing TWP concentrations (Ø 24 µg TWP vs. 107 µg MP per kg sediment (dry weight); Ø 126 µg TWP vs. 378 µg MP per kg marine salt) or were no longer present (blue mussels), while "traditional" polymers were still ubiquitously distributed.