Py-GC-MS analysis for microplastics: Unlocking matrix challenges and sample recovery when analyzing wastewater for polypropylene and polystyrene.

Matrix interference and recovery when using pyrolysis gas chromatography (Py-GC-MS) to analyze wastewater for polystyrene (PS) and polypropylene (PP) microplastics (MP) was studied. Raw wastewater underwent a sample preparation train commonly applied for such matrix. The train consisted of six discrete steps to reduce the organic matter content without affecting MP in the sample. One large wastewater sample was collected, homogenized, and subdivided into 21 subsamples. Three samples were analyzed without further sample preparation. The remaining samples were divided in sets of three, and each set underwent an increasing number of steps of the procedure, up to the last set, which underwent the full treatment. The matrix effect on the determination of PS and PP was statistically evaluated by comparing in-matrix and external calibration curves at each step. Recovery of MP was assessed after each step by adding deuterated PS to the samples. A main finding was that there was no significant matrix effect for these polymers throughout the preparation train, suggesting that matrix components did not interfere with the analytical method. However, a significant loss of polymer mass was found between the steps, which may result in MPs falling below detection limits. Therefore, Py-GC-MS could be used for MP quantification before analysis by other techniques which require more extensive matrix removal. A downside of this approach is that analyzing such samples without matrix reduction will increase the need for instrumental maintenance.

Pinaceae Pine Resins (Black Pine, Shore Pine, Rosin, and Baltic Amber) as Natural Dielectrics for Low Operating Voltage, Hysteresis-Free, Organic Field Effect Transistors.

Four pinaceae pine resins analyzed in this study: black pine, shore pine, Baltic amber, and rosin demonstrate excellent dielectric properties, outstanding film forming, and ease of processability from ethyl alcohol solutions. Their trap-free nature allows fabrication of virtually hysteresis-free organic field effect transistors operating in a low voltage window with excellent stability under bias stress. Such green constituents represent an excellent choice of materials for applications targeting biocompatibility and biodegradability of electronics and sensors, within the overall effort of sustainable electronics development and environmental friendliness.

Seeping plastics: Potentially harmful molecular fragments leaching out from microplastics during accelerated ageing in seawater.

Microplastics are the particulate plastic debris found almost everywhere as environmental contaminants. They are not chemically stable persistent pollutants, but reactive materials. In fact, synthetic polymers exposed to the environment undergo chemical and physical degradation processes which lead not only to mechanical but also molecular fragmentation, releasing compounds that are potentially harmful for the environment and human health. We carried out accelerated photo-oxidative ageing of four reference microplastics (low- and high-density polyethylene, polypropylene, and polystyrene) directly in artificial seawater. We then made a characterization at the molecular level along with a quantification of the chemical species leached into water. Gas chromatography/mass spectrometry analyses performed after selective extraction and derivatization enabled us to identify more than 60 different compounds. Analysis of the leachates from the three polyolefins revealed that the main degradation products were mono- and dicarboxylic acids, along with linear and branched hydroxy acids. The highest amount of leached degradation species was observed for polystyrene, with benzoic acid and phenol derivatives as the most abundant, along with oligomeric styrene derivatives. The results from reference microplastics were then compared with those obtained by analyzing leachates in artificial seawater from aged plastic debris collected in a natural environment. The differences observed between the reference and the environmental plastic leachates mainly concerned the relative abundances of the chemical species detected, with the environmental samples showing higher amounts of dicarboxylic acids and oxidized species.

Co-pyrolysis of biomass and plastic: Synergistic effects and estimation of elemental composition of pyrolysis oil by analytical pyrolysis-gas chromatography/mass spectrometry.

This paper presents a study on the pyrolytic behavior of mixtures of lignocellulosic biomass with hydrocarbon plastics using analytical pyrolysis-GC/MS. Semi-quantitative analysis using chromatographic peak areas was used to investigate the composition of the pyrolysis oils and to highlight the occurrence of synergistic effects. A new method is also proposed to estimate the elemental composition of the pyrolysis oil based on the peak areas and brute formulas of the pyrolysis products. The results indicate that synergistic effects during co-pyrolysis favor secondary pyrolysis of holocellulose and polystyrene oligomers, and hinder radical chain-scission of polyethylene chains. H/C and O/C values of the pyrolysis oils were improved by the addition of plastic, indicating a decrease in the content of oxygenated pyrolysis products. The best performances were observed for the mixture containing 70% fir wood and 30% polyethylene, in which synergistic effects led to both an increase of H/C and a decrease of O/C.

A Systematic Study on the Degradation Products Generated from Artificially Aged Microplastics.

Most of the analytical studies focused on microplastics (MPs) are based on the detection and identification of the polymers constituting the particles. On the other hand, plastic debris in the environment undergoes chemical and physical degradation processes leading not only to mechanical but also to molecular fragmentation quickly resulting in the formation of leachable, soluble and/or volatile degradation products that are released in the environment. We performed the analysis of reference MPs-polymer micropowders obtained by grinding a set of five polymer types down to final size in the 857-509 µm range, namely high- and low-density polyethylene, polystyrene (PS), polypropylene (PP), and polyethylene terephthalate (PET). The reference MPs were artificially aged in a solar-box to investigate their degradation processes by characterizing the aged (photo-oxidized) MPs and their low molecular weight and/or highly oxidized fraction. For this purpose, the artificially aged MPs were subjected to extraction in polar organic solvents, targeting selective recovery of the low molecular weight fractions generated during the artificial aging. Analysis of the extractable fractions and of the residues was carried out by a multi-technique approach combining evolved gas analysis-mass spectrometry (EGA-MS), pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS), and size exclusion chromatography (SEC). The results provided information on the degradation products formed during accelerated aging. Up to 18 wt% of extractable, low molecular weight fraction was recovered from the photo-aged MPs, depending on the polymer type. The photo-degradation products of polyolefins (PE and PP) included a wide range of long chain alcohols, aldehydes, ketones, carboxylic acids, and hydroxy acids, as detected in the soluble fractions of aged samples. SEC analyses also showed a marked decrease in the average molecular weight of PP polymer chains, whereas cross-linking was observed in the case of PS. The most abundant low molecular weight photo-degradation products of PS were benzoic acid and 1,4-benzenedicarboxylic acid, while PET had the highest stability towards aging, as indicated by the modest generation of low molecular weight species.

A genome sequence from a modern human skull over 45,000 years old from Zlatý kun in Czechia.

Modern humans expanded into Eurasia more than 40,000 years ago following their dispersal out of Africa. These Eurasians carried ~2-3% Neanderthal ancestry in their genomes, originating from admixture with Neanderthals that took place sometime between 50,000 and 60,000 years ago, probably in the Middle East. In Europe, the modern human expansion preceded the disappearance of Neanderthals from the fossil record by 3,000-5,000 years. The genetic makeup of the first Europeans who colonized the continent more than 40,000 years ago remains poorly understood since few specimens have been studied. Here, we analyse a genome generated from the skull of a female individual from Zlatý kun, Czechia. We found that she belonged to a population that appears to have contributed genetically neither to later Europeans nor to Asians. Her genome carries ~3% Neanderthal ancestry, similar to those of other Upper Palaeolithic hunter-gatherers. However, the lengths of the Neanderthal segments are longer than those observed in the currently oldest modern human genome of the ~45,000-year-old Ust'-Ishim individual from Siberia, suggesting that this individual from Zlatý kun is one of the earliest Eurasian inhabitants following the expansion out of Africa.

Molecular profiling of Peru Balsam reveals active ingredients responsible for its pharmaceutical properties.

Peru Balsam, a resinous substance derived from Myroxylon balsamum var. pereirae, has historically been used as a topical ointment for various skin conditions such as scabies, poorly healing wounds, eczema, and haemorrhoids. The ingredients responsible for these properties are not fully elucidated. We investigated the chemical composition of two Peru Balsam samples, one historical and one modern, using gas chromatography/mass spectrometry to identify the active ingredients responsible for its pharmaceutical properties. Both Peru Balsam specimens investigated had similar compositions, showing the stability of the substance. Components identified are effective against scabies, exhibit antimicrobial activity and aid skin penetration. These properties are consistent with historical uses of Peru Balsam. Several ingredients are also known allergens. This study, combining chemical information with scientific literature related to pharmaceutical properties of natural substances, represents a breakthrough in the elucidation of active ingredients in Peru Balsam.

Microwave-assisted solvent extraction and double-shot analytical pyrolysis for the quali-quantitation of plasticizers and microplastics in beach sand samples.

Pollution from microplastics (MPs) needs to be evaluated by deploying reliable analytical techniques that provide qualitative and quantitative data on the extent of contamination in the various environmental matrices. Solvent extraction of MPs followed by pyrolysis-gas chromatography-mass spectrometry (Py-GC-MS) provides data that not only regard the soluble plastics, but also the organic additives contained in MPs and the low-molecular weight degradation products of insoluble plastics. In this study, the potential of microwave-assisted solvent extraction and double-shot Py-GC-MS was investigated in order to obtain quali-quantitative information on polystyrene and on phthalate plasticizers in environmental samples. The method was validated and provided recoveries higher than 96 %, and detection limits lower than 1 ng and 1 µg for phthalates and polystyrene, respectively. We used the method to analyze samples of sand collected from a shoreline in Tuscany (central Italy) and thereby determine the content of phthalates and polystyrene at different depths and distances from the coastline. Qualitative data were also obtained regarding the presence of oxidation products derived from polyethylene and polypropylene. The different contents of plasticizers, plastics, and degradation products in the investigated samples are discussed in relation to how environmental agents affect the leaching and degradation processes of the polymers.

A Mass Spectrometric Study on Tannin Degradation within Dyed Woolen Yarns.

Natural tannins from various plants have been used throughout human history in textile dyeing, often as mordant dyes. The ageing behavior of these dyes is a challenge in conservation science, requiring a thorough knowledge of the textile-mordant-dye system. In this work, we analyzed reference wool yarns dyed with natural tannins from oak gallnuts, walnut (Juglans regia), and catechu (Acacia catechu), after artificial ageing. To gain insights on the composition of the dyestuffs and on how they aged, an analytical procedure based on extraction with Na2EDTA/DMF (ethylenediaminetetraacetic acid/dimethylformamide) and high-performance liquid chromatography (HPLC) analysis using high-resolution mass spectrometry detection was used. Since conventional reversed-phase (RP) columns usually show poor retention efficiency of highly polar compounds such as tannins, an RP-amide embedded polar group stationary phase was used to achieve optimal retention of the most polar compounds. Tannins from oak gallnuts showed little degradation after ageing, while a significant increase in the content of hydroxybenzoic acids was observed for tannins from walnut and catechu. Finally, the analytical procedure was applied to characterize the tannin dyes in historical tapestries from the 15th to 16th century, and the results were discussed in comparison with the reference yarns.

Olive mill wastewaters: quantitation of the phenolic content and profiling of elenolic acid derivatives using HPLC-DAD and HPLC/MS2 with an embedded polar group stationary phase.

Olive mill wastewaters (OMWs) are important by-products of olive oil production. The wide availability and the forbidding economic costs of OMWs disposal have generated interest in their possible exploitation as a sustainable source of polyphenols. The development and optimisation of improved analytical methods for the detailed characterisation of polyphenol molecular profiles after production and during storage conditions are thus required. A new analytical method based on reverse-phase HPLC separation of polyphenols in OMWs on an embedded-polar group (EPG) stationary phase is proposed as an alternative to conventional C18 columns. The procedure was used for the quantitation of 11 polyphenols, using diode-array detection (DAD), and achieving quantitation limits equal to or lower than 0.1 µg g-1. The same chromatographic set-up, coupled with high resolution tandem mass spectrometry (HPLC/ESI-Q-ToF), allowed us to identify hydroxytyrosyl esters of elenolic acid, whose relative abundance is proposed for monitoring the ageing of OMWs during storage.

Effect of ball-milling on crystallinity index, degree of polymerization and thermal stability of cellulose.

A combined study of crystallinity index (CI), degree of polymerisation (DP) and thermal stability of cellulose was carried out for monitoring the effect of ball-milling. DP and CI are two fundamental quantities that describe the physico-chemical behaviour of cellulose. Milling is a common strategy to reduce cellulose crystallinity. In this work, four different commercially available celluloses were milled at 30, 60 and 120 min, and the changes in DP and CI were monitored using spectroscopic, diffraction and chromatographic techniques. Evolved gas analysis-mass spectrometry (EGA-MS) was also used to evaluate the changes in apparent activation energy (Ea) of the pyrolysis reaction upon different milling times by using model-free isoconversional methods. The results showed substantial decrease in CI values and moderate changes in DP after two-hours of ball-milling. Ea were found in the range 110-140 kJ/mol, and were reduced by 10% on average after two hours of ball-milling.

A comparison of fast and reactive pyrolysis with insitu derivatisation of fructose, inulin and Jerusalem artichoke (Helianthus tuberosus).

Reactive pyrolysis is a technique that provides mechanistic information by performing pyrolysis of the substrate in a sealed glass capsule at elevated temperature and pressure for relatively long time. This technique has already shown great potential for the analysis of biomass, favouring the formation of only the most thermostable compounds. In this work, both fast and reactive pyrolysis with on-line gas chromatography-mass spectrometry analysis (Py-GC/MS) are used to study fructose, inulin and Jerusalem artichoke tubers (Heliantus tuberosus). Interesting differences were found between the two systems, and became even more evident as the reaction time was increased. The most striking result was the formation of di-fructose dianhydrides (DFAs), a class of compounds with interesting biological activities. DFAs were obtained in high yields from reactive pyrolysis, but not from fast pyrolysis. Hypotheses on the pyrolysis mechanisms were made based upon the composition of the pyrolysates. This work describes for the first time the behaviour of fructans under reactive pyrolysis.

Antihyperlipidemic effect of a Rhamnus alaternus leaf extract in Triton-induced hyperlipidemic rats and human HepG2 cells.

The Mediterranean buckthorn, Rhamnus alaternus L., is a plant used in traditional medicine in Mediterranean countries. We aimed at characterizing its phenolic compounds and explore potential antihyperlipidemic activity of this plant. The profile of phenolic compounds in R. alaternus leaf crude methanolic extract (CME) and its liquid-liquid extraction-derived fractions were analyzed by high-performance liquid chromatography/electrospray ionization tandem mass spectrometry (HPLC/ESI-MS2). Effects of CME on: circulating lipids in rats with Triton WR-1339-induced hyperlipidemia, intracellular lipid accumulation and expression of genes of fatty acid metabolism in human hepatoma HepG2 cells, and adipogenesis in the 3T3-L1 murine adipocyte cell model were assessed. The HPLC/ESI-MS2 analytical profile revealed a total of fifteen compounds, of which eleven were identified. Oral CME administration decreased blood levels of cholesterol and triacylglycerols in hyperlipidemic rats (by 60% and 70%, respectively, at 200 mg CME/kg). In HepG2 cells, CME exposure dose-dependently decreased intracellular lipids and up-regulated gene expression of carnitine palmitoyltransferase 1 involved in fatty acid oxidation. In the 3T3-L1 model, CME favored preadipocyte proliferation and adipogenesis, pointing to positive effects on adipose tissue expandability. These results suggest novel uses of R. alaternus by showing that its leaves are rich in flavonoids and flavonoid derivatives with an antihyperlipidemic effect in vivo and in hepatic cells.

Timing in Analytical Pyrolysis: Py(HMDS)-GC/MS of Glucose and Cellulose Using Online Micro Reaction Sampler.

A novel analytical approach based on pyrolysis-gas chromatography coupled with mass spectrometry of carbohydrates with in situ silylation using hexamethyldisilazane is presented in this work for the first time. A micro reaction sampler was used to simultaneously achieve the pyrolyis reaction and facilitate the derivatization of pyrolysis products, by enabling the materials to react with the derivatizing agent in a sealed capsule at high temperature and pressure for long periods of time. This drastically increased the complete silylation of the pyrolysis products and the chromatographic resolution, resulting in less complex pyrograms and increased sensitivity toward the most stable compounds. Different results were obtained for glucose and cellulose in terms of predominant pyrolytic pathways. The formation of anhydrosugars was the preferential pyrolytic reaction for glucose, while the formation of cyclopentenones and small molecules was predominant for the pyrolysis of cellulose. Steric hindrance effects of polysaccharide chains on the efficiency of the derivatizing agent were hypothesized in order to explain the different results. A good reproducibility was found, with relative standard deviations not greater than 10%. Semiquantitative calculations showed that the partial silylation of anhydrosugars was almost completely overcome after 10 min of reactive pyrolysis. This work discloses a powerful and potentially widely applicable analytical method for the investigations of organic materials under controlled pyrolytic conditions, with the advantage of increasing the effectiveness of in situ derivatization.