Riverine suspended matter (river-SPM) contains large amounts of natural particles consisting of cellulose and lignin, posing a challenge for microplastic (MPs) analysis. Additionally, organic matter composition under seasonal and discharge-related dynamics varies for each river. Therefore, this study attempted to identify a universally applicable clean-up procedure to remove matrix particles with high organic matter content, mainly plant debris, from the river-SPM samples. This study tested six digestion procedures adapted from existing (ligno)cellulosic digestion/oxidation methods with a river-SPM sample followed by density separation using sodium polytungstate. From these, NaOCl treatment (CL) showed the highest efficiency of organic matter removal, eliminating 96-100 % of the matrix weight. Exposure of tested MPs (in size range of 100-500 μm) in the CL protocol showed no adverse effect on polypropylene (PP), polyethylene (PE), polystyrene (PS), and polyethylene terephthalate (PET). Similarly, no detrimental matrix effects were found on 100 μm spherical PS standard particles spiked in the river-SPM. This procedure achieved high recovery rates of tested plastics (92-100 %). In terms of method applicability, the procedure was successfully applied to samples from different seasons containing various matrix concentrations and compositions. Although samples with high amounts of plant debris needed to undergo this procedure twice, only minor alteration of the particle surface and IR spectrum of PS presented and no adverse effect on PP. To further tackle the high and varied concentration of plant-derived matrix in river-SPM samples, a novel sequential oxidation protocol (2DOCL) combining cellulose dissolution, Fenton's oxidation, and NaOCl oxidation was developed, resulting in a more (time) effective and predictable process, demonstrating no severely destructive effect on tested plastics. The sequential digestion protocol can be optimized for certain matrices as applying all steps will not be necessary.
It has been established that various anthropogenic contaminants have already reached all the world's pristine locations, including the polar regions. While some of those contaminants, such as lead and soot, are decreasing in the environment, thanks to international regulations, other novel contaminants emerge. Plastic pollution has been shown as a durable novel pollutant, and, since recently, smaller and smaller plastics particles have been identified in various environments (air, water and soil). Considerable research already exists measuring the plastics in the 5 mm to micrometre size range (microplastics). However, far less is known about the plastics debris that fragmented to the sub-micrometre size (nanoplastics). As these small particles are light, it is expected that they have already reached the most remote places on Earth, e.g. transported across the globe by air movement. In this work, we used a novel method based on Thermal Desorption - Proton Transfer Reaction - Mass Spectrometry (TD-PTR-MS) to detect and measure nanoplastics of different types in the water sampled from a Greenland firn core (T2015-A5) and a sea ice core from Antarctica. We identify polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polystyrene (PS), polyvinyl chloride (PVC), and Tire wear nanoparticles in the 14 m deep Greenland firn core and PE, PP and PET in sea ice from Antarctica. Nanoplastics mass concentrations were on average 13.2 ng/mL for Greenland firn samples and 52.3 ng/mL for Antarctic sea ice. We further discuss the possible sources of nanoplastics that we found at these remote locations, which likely involve complex processes of plastic circulation (emission from both land and sea surface, atmospheric and marine circulation).
<p>Currently, little is understood about the deposition and re-volatilisation of organic matter (OM) in snow. Understanding this balance for individual organic compounds has the potential to provide important information about present and past atmospheric conditions. This research investigates in detail the deposition and re-volatilisation rates for speci&#64257;c atmospheric OM that are present in alpine snow. Captured in the blank canvas of snow, any dissolved organic matter (DOM) in surface snow will re&#64258;ect the relative abundances in the atmosphere once their deposition and revolatilisation rates are known. Likewise, DOM e&#64256;ectively preserved in glacial ice will also express relative atmospheric composition of past climates. A recent pilot study by D. Materi&#263; et al.[1] investigates the post-precipitation change of OM in snow near the Sonnblick Observatory in the Austrian Alps. Using proton transfer reaction mass spectrometry, surface snow samples taken over several days were analyzed, and any organics found were grouped by their similar dynamics. This research expands on this study by analyzing snow samples over a larger spatial domain around Sonnblick during the course of &#64257;ve days in conjunction with long-term snow sampling currently underway at the observatory. Together, analysis of these samples will reveal changes in OM in surface snow over the course of the entire melt season. This research also considers both &#64257;ltered and un&#64257;ltered snow samples to di&#64256;erentiate and identify OM of di&#64256;erent sizes that are present within each sample. Long-term measurements of post-precipitation OM in surface snow will provide more coherent trends for deposition and re-volatilisation rates of organics, which can be used to tie future measurements of DOM in surface snow to atmospheric OM.</p>
Abstract. In September 2017, we conducted the Proton-transfer-reaction mass-spectrometry (PTR-MS) Intercomparison campaign at CABauw (PICAB), a rural site in central Netherlands. Nine research groups deployed a total of eleven instruments covering a wide range of instrument types and performance. We applied a new calibration method based on fast injection of a gas standard through a sample loop. This approach allows calibrations on time scales of seconds and within a few minutes an automated sequence can be run allowing to retrieve diagnostic parameters that indicate the performance status. We developed a method to retrieve the mass dependent transmission from the fast calibrations, which is an essential characteristic of PTR-MS instruments, limiting the potential to calculate concentrations based on counting statistics and simple reaction kinetics in the reactor/drift tube. Our measurements show that PTR-MS instruments follow the simple reaction kinetics if operated in the standard range for pressures and temperature of the reaction chamber (i.e. 1–4 mbar, 30–120 ℃, respectively), and a reduced field strength E/N in the range of 100–160 Td. If artefacts can be ruled out, it becomes possible to quantify the signals of uncalibrated organics with accuracies better than ±30 %. The simple reaction kinetics approach produces less accurate results at E/N levels below 100 Td, because significant fractions of primary ions form water hydronium clusters. De-protonation through reactive collisions of protonated organics with water molecules need to be considered when the collision energy is a substantial fraction of the exoergicity of the proton transfer reaction, and/or if protonated organics undergo many collisions with water molecules.
The chemical and stable carbon isotopic composition of the organic aerosol particles (OA) emitted by a shuttle passenger ship between mainland Naples and island Capri in Italy were investigated. Various methylsiloxanes and derivatives were found in particulate ship emissions for the first time, as identified in the mass spectra of a thermal desorption - proton transfer reaction - mass spectrometer (TD-PTR-MS) based on the natural abundance of silicon isotopes. Large contributions of methylsiloxanes to OA (up to 59.3%) were found under inefficient combustion conditions, and considerably lower methylsiloxane emissions were observed under cruise conditions (1.2% of OA). Furthermore, the stable carbon isotopic composition can provide a fingerprint for methylsiloxanes, as they have low δ13C values in the range of -44.91‰ ± 4.29‰. The occurrence of methylsiloxanes was therefore further supported by low δ13C values of particulate organic carbon (OC), ranging from -34.7‰ to -39.4‰, when carbon fractions of methylsiloxanes in OC were high. The δ13C values of OC increased up to around -26.7‰ under cruise conditions, when carbon fractions of methylsiloxanes in OC were low. Overall, the δ13C value of OC decreased linearly with increasing carbon fraction of methylsiloxanes in OC, and the slope is consistent with a mixture of methylsiloxanes and fuel combustion products. The methylsiloxanes in ship emissions may come from engine lubricants.
Nanoplastics are suspected to pollute every environment on Earth, including very remote areas reached via atmospheric transport. We approached the challenge of measuring environmental nanoplastics by combining high-sensitivity TD-PTR-MS (thermal desorption-proton transfer reaction-mass spectrometry) with trained mountaineers sampling high-altitude glaciers ("citizen science"). Particles < 1 μm were analysed for common polymers (polyethylene, polyethylene terephthalate, polypropylene, polyvinyl chloride, polystyrene and tire wear particles), revealing nanoplastic concentrations ranging 2–80 ng mL− 1 at five of 14 sites. The dominant polymer types found in this study were tire wear, polystyrene and polyethylene particles (41%, 28% and 12%, respectively). Lagrangian dispersion modelling was used to reconstruct possible sources of micro- and nanoplastic emissions for those observations, which appear to lie largely to the west of the Alps. France, Spain and Switzerland have the highest contributions to the modelled emissions. The citizen science approach was found to be feasible providing strict quality control measures are in place, and is an effective way to be able to collect data from remote and inaccessible regions across the world.
Abstract. The exchange of organic matter (OM) between the atmosphere and snow is poorly understood due to the complex nature of OM and the convoluted processes of deposition, re-volatilisation, and chemical and biological processing. OM that is finally retained in glaciers potentially holds a valuable historical record of past atmospheric conditions; however, our understanding of the processes involved is insufficient to translate the measurements into an interpretation of the past atmosphere. This study examines the dynamic processes of post-precipitation OM change at the alpine snow surface with the goal of interpreting the processes involved in surface snow OM.
Proton Transfer Reaction - Mass Spectrometry (PTR-MS) is a sensitive, soft ionisation method suitable for qualitative and quantitative analysis of volatile and semi-volatile organic vapours. PTR-MS is used for various environmental applications including monitoring of volatile organic compounds (VOCs) emitted from natural and anthropogenic sources, chemical composition measurements of aerosols, etc. Here we apply thermal desorption PTR-MS for the first time to characterise the chemical composition of dissolved organic matter (DOM). We developed a clean, low-pressure evaporation/sublimation system to remove water from samples and coupled it to a custom-made thermal desorption unit to introduce the samples to the PTR-MS. Using this system, we analysed waters from intact and degraded peat swamp forest of Kalimantan, Indonesian Borneo, and an oil palm plantation and natural forest in Sarawak, Malaysian Borneo. We detected more than 200 organic ions from these samples and principal component analysis allowed clear separation of the different sample origins based on the composition of organic compounds. The method is sensitive, reproducible, and provides a new and comparatively cheap tool for a rapid characterisation of water and soil DOM.
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