Influence of surface oxidation on the quantification of polypropylene microplastics by pyrolysis gas chromatography mass spectrometry.

The influence of photo-oxidation on the quantification of isotactic polypropylene by Pyrolysis Gas Chromatography/Mass Spectrometry (Pyr-GC/MS) was assessed. Beads (oval shape, ~5 mm) and fragments (irregular shaped, 250-50 µm and 500-1000 µm) were subjected to relatively harsh simulated accelerated weathering conditions (using a filtered xenon-arc reproducing sunlight's full spectrum) for up to 37 and 80 days, respectively. Samples collected (n = 10 replicates for each treatment) at increasing number of weathering days were analysed by Fourier-transform infrared spectroscopy with Attenuated Total Reflection (FTIR-ATR), scanning electron microscopy, and differential scanning calorimetry in order to assess the extent and the rate of degradation. The rate of surface oxidation occurred faster for fragments compared to beads, probably due to their higher surface area. Quantification of the polypropylene trimer (2,4-dimethyl-1-heptene) via double shot Pyr-GC/MS, showed that the signal of the trimer relative to the mass of polypropylene was reduced through weathering with a degradation rate of 1:3 faster for fragments over beads. Signal reduction and carbonyl index were correlated to show that polypropylene with a carbonyl index of ≥13 has a significantly reduced 2,4-dimethyl-1-heptene signal when compared to virgin material. Consequently, the quantification of polypropylene subjected to weathering under harsh conditions may be underestimated by 42% (fragments, carbonyl index: 18) to 49% (beads, carbonyl index: 30) when quantified by Pyr-GC/MS and using virgin polypropylene calibration standards. Pyrolysis at a lower temperature (350 °C) identified six degradation specific markers (oxidation products) that increased in concentration with weathering. Further comparisons between virgin and weathered microplastics may need to be considered to avoid underestimation of microplastic concentrations in future studies.

Plastics contamination of store-bought rice.

This study investigated mass concentrations of selected plastics in store-bought rice, the staple of more than half the world's population. Polyethylene, polyethylene terephthalate, poly-(methyl methacrylate), polypropylene, polystyrene and polyvinyl chloride were quantified using pressurized liquid extraction coupled to double-shot pyrolysis gas chromatography/mass spectrometry. Polyethylene, polypropylene and polyethylene terephthalate were quantifiable in the rice samples with polyethylene the most frequently detected (95%). There was no statistical difference between total plastic concentration in paper and plastic packaged rice. Shaking the rice in its packaging had no significant difference on the concentration of plastics. Washing the rice with water significantly reduced plastic contamination. Instant (pre-cooked) rice contained fourfold higher levels of plastics, suggesting that industrial processing potentially increases contamination. A preliminary estimate of the intake of plastic through rice consumption for Australians established 3.7 mg per serve (100 g) if not washed and 2.8 mg if washed. Annual consumption was estimated around 1 g/person.

Quantitative Analysis of Selected Plastics in High-Commercial-Value Australian Seafood by Pyrolysis Gas Chromatography Mass Spectrometry.

Microplastic contamination of the marine environment is widespread, but the extent to which the marine food web is contaminated is not yet known. The aims of this study were to go beyond visual identification techniques and develop and apply a simple seafood sample cleanup, extraction, and quantitative analysis method using pyrolysis gas chromatography mass spectrometry to improve the detection of plastic contamination. This method allows the identification and quantification of polystyrene, polyethylene, polyvinyl chloride, polypropylene, and poly(methyl methacrylate) in the edible portion of five different seafood organisms: oysters, prawns, squid, crabs, and sardines. Polyvinyl chloride was detected in all samples and polyethylene at the highest total concentration of between 0.04 and 2.4 mg g-1 of tissue. Sardines contained the highest total plastic mass concentration (0.3 mg g-1 tissue) and squid the lowest (0.04 mg g-1 tissue). Our findings show that the total concentration of plastics is highly variable among species and that microplastic concentration differs between organisms of the same species. The sources of microplastic exposure, such as packaging and handling with consequent transference and adherence to the tissues, are discussed. This method is a major development in the standardization of plastic quantification techniques used in seafood.

Identification and quantification of selected plastics in biosolids by pressurized liquid extraction combined with double-shot pyrolysis gas chromatography-mass spectrometry.

The identification and quantification of selected plastics (polystyrene (PS), polycarbonate (PC), poly-(methyl methacrylate) (PMMA), polypropylene (PP), polyethylene terephthalate (PET), polyethylene (PE) and polyvinyl chloride (PVC)) in biosolids (treated sewage sludge) was performed by pressurized liquid extraction (PLE) combined with double-shot pyrolysis gas chromatography-mass spectrometry. Validation of the method yielded recoveries of between 85 and 128% (mean RSD 11%) at a linear range of between 0.01 and 2 µg. The distribution of plastics within 25 biosolid samples from a single wastewater treatment plant in Australia was assessed. The mass concentration of PE, PVC, PP, PS and PMMA was between 0.1 and 4.1 mg/g dry weight (dw) across all samples, with a total plastic concentration Æ©Plastics of between 2.8 and 6.6 mg/g dw (median = 4.1 mg/g dw). PE was the predominant plastic detected (mean concentration of 2.2 mg/g dw), contributing to 50% of the total of all plastics. Overall, this study demonstrates that pressurized liquid extraction (PLE) combined with double-shot pyrolysis gas chromatography-mass spectrometry can be used to identify and quantify PE, PP, PVC, PS, and PMMA in biosolids.

[4+2] cycloaddition reactions between 1,8-disubstituted cyclooctatetraenes and diazo dienophiles: stereoelectronic effects, anticancer properties and application to the synthesis of 7,8-substituted bicyclo[4.2.0]octa-2,4-dienes.

A detailed examination of [4+2] cycloaddition reactions between 1,8-disubstituted cyclooctatetraenes and diazo compounds revealed that 4-phenyl-1,2,4-triazole-3,5-dione (PTAD) reacts to form either 2,3- or 3,4-disubstituted adducts. The product distribution can be controlled by modulating the electron density of the cyclooctatetraene. Unprecedented [4+2] cycloadditions between diisopropyl azodicarboxylate (DIAD) and 1,8-disubstituted cyclooctatetraenes are also described and further manipulation of a resulting cycloadduct uncovered a new pathway to the synthetically challenging bicyclo[4.2.0]octa-2,4-diene family. Variation of the substituents resulted in a range of compounds displaying selective action against different human tumour cell types.

Experimental determination of the gas phase proton affinities of the conjugate base anions of 2-iodoxybenzoic acid (IBX) and 2-iodosobenzoic acid (IBA).

The gas phase anion proton affinities of the periodinane anions IBX- and IBA- were examined using mass spectrometry-based experiments, and estimated as 1300 +/- 25 and 1390 +/- 10 kJ mol(-1), respectively. The experimental results were supported by theoretical calculations, which yielded proton affinities of 1336 and 1392 kJ mol(-1) for IBX- and IBA- respectively, at the B3LYP/aug-cc-PVDZ level of theory.