Analytical strategy to assess the microbial degradation of poly(butylene-adipate-co-terephthalate)/poly(lactic acid) films.

Plastic is widely used in agricultural applications, but its waste has an adverse environmental impact and a long-term detrimental effect. The development of biodegradable plastics for agricultural use is increasing to mitigate plastic waste. The most commonly used biodegradable plastic is poly(butylene adipate co-terephthalate)/poly(lactic acid) (PBAT/PLA) polymer. In this study, an analytical procedure based on dispersive liquid-liquid microextraction (DLLME) followed by gas chromatography-mass spectrometry (GC-MS) in combination with chemometrics has been optimized to assess the degradation level of PBAT/PLA films by monitoring their characteristic degradation products. Carboxylic acids (benzoic, phthalic, adipic, heptanoic, and octadecanoic acids) and 1,4-butanediol have been found to be potential markers of PBAT/PLA degradation. The DLLME-GC-MS analytical approach has been applied for the first time to assess the degradation efficiency of several microorganisms used as degradation accelerators of PBAT/PLA based on the assigned potential markers. This analytical strategy has shown higher sensitivity and precision than standard techniques, such as elemental analysis, allowing us to detect low degradation levels.

Effect of Abiotic Treatments on Agricultural Plastic Waste: Efficiency of the Degradation Processes.

In this study, four different plastic materials usually used in the agricultural sector (polystyrene film (PS), polyethylene terephthalate film (PET), low-density polyethylene film (LDPE) and linear low-density polyethylene film (LLDPE)) were subjected to different abiotic treatments, including photo-oxidation (ultraviolet and e-beam radiation) and thermochemical treatments, to enhance polymer degradation. The extensive use of these polymers leads to large amounts of plastic waste generation, including small plastic pieces, known as microplastics, which affect the quality of the agricultural environment, including soil fertility and quality. Therefore, polymer degradation strategies are needed to effectively reduce plastic waste to protect the agricultural sector. The degree of polymer degradation was assessed by the use of thermal and spectroscopic analyses, such as TGA and FTIR. In addition, efficiency, cost-benefits, and potential side-effects were also evaluated to propose the optimal degradation strategy to reduce plastic waste from the point of view of efficiency. The results obtained showed that the pre-treatments based on photo-oxidation (ultraviolet B and C and e-beam radiation) were more efficient and had a better cost-benefit for the degradation of the polymers studied in relation to the thermochemical treatments. Specifically, ultraviolet photo-oxidation worked well for PS and PET, requiring low energy and medium times. However, e-beam radiation was recommended for PE (LDPE and LLDPE) degradation, since high energy and long times were needed when ultraviolet energy was applied to this polymer. Furthermore, the overall efficiency of the plastic degradation of pre-treatments should be studied using a multicriteria approach, since FTIR assessments, in some cases, only consider oxidation processes on the plastic surface and do not show the potential integrity changes on the plastic probes.

Determination of extractable pollutants from microplastics to vegetables: Accumulation and incorporation into the food chain.

The presence and impacts of microplastics (MPs) are being extensively researched and reviewed, especially in the marine environment. However, mobility, transportation routes, and accumulation of leaching compounds such as additives in plastic waste including MPs are scarcely studied. Information regarding ecotoxicity and leachability of compounds related to MPs contamination in the environment is limited. Current work presents the levels of leachates from plastic materials in edible-root and non-edible root vegetables. Samples were analyzed by static headspace and gas chromatography-mass spectrometry (SHS-GC-MS) and the presence of 93 putative compounds was accurately monitored in the samples by the usage of Mass Spectrometry-Data Independent Analysis software. The application of chemometrics to the SHS-GC-MS dataset allowed differentiation between the levels of plastic related compounds in edible root and non-edible root vegetables, the former showing a higher content of plastic leachates. For SHS sampling, 3 g of the sample were incubated at 130 °C for 35 min in the HS vial and toluene and naphthalene were added as internal standards for quantification purposes. The developed SHS-GC-MS methodology is straightforward, reliable, and robust and allowed the quantification of sixteen plastic associated compounds in the samples studied in a range from 0.14 to 28800 ng g-1 corresponding to 2,4-di-tert-butylphenol and p,α-dimethylstyrene, respectively. Several of the quantified compounds pointed out to potential contamination of polystyrene and/or polyvinyl chloride MPs.

A novel application of thermogravimetry-mass spectrometry for polystyrene quantification in the PM10 and PM2.5 fractions of airborne microplastics.

Microplastics have appeared as emerging pollutants due to the diverse applications of plastics in today's world. Growing evidence points to the negative impacts that airborne microplastics have on human health, as they can enter the human body through respiration. Our aim was to quantify polystyrene airborne microplastics in smaller fractions, thoracic (PM10) and alveolar (PM2.5), as they have scarcely been studied. In this work, we proposed a methodology based on thermogravimetric analysis coupled with mass spectrometry that requires minimal sample preparation and does not limit particle size. We applied this methodology to quantify the airborne polystyrene in PM10 and PM2.5 fractions in mass units of microplastics per m3 of air in an urban and agricultural region during the summer of 2021. The mean concentrations of polystyrene found in the PM10 and PM2.5 fractions were 2.09 and 1.81 ng m-3, respectively. Therefore, the majority of airborne polystyrene microplastics are found in the alveolar fraction which, is associated with severe cardiopulmonary and respiratory diseases. According to air mass backward trajectories, it was noted that the main sources of these emerging pollutants could be related to local agricultural practices.

Thermogravimetry coupled with mass spectrometry successfully used to quantify polyethylene and polystyrene microplastics in organic amendments.

The global consumption of plastic is growing year by year, producing small plastic pieces known as microplastics (MPs) that adversely affect ecosystems. The use of organic amendments (compost and manure) polluted with MPs affects the quality of agricultural soils, and these MPs can be incorporated into the food chain and negatively impact human health. Current European legislation only considers large plastic particles in organic amendments. There is no information regarding MP pollution. Thus, the development of a methodology to support future legislation ensuring the quality of agricultural soils and food safety is necessary. This proposed methodology is based on thermogravimetry coupled with mass spectrometry to quantify polyethylene and polystyrene (PE and PS) MPs through their mass spectrometry signal intensity of characteristic PE (m/z 41, 43 and 56) and PS (m/z 78 and 104) ions. This method has been validated with several organic amendments where the MP content ranged from 52.6 to 4365.7 mg kg-1 for PE-MPs and from 1.1 to 64.3 mg kg-1 for PS-MPs. The proposed methodology is a quick and robust analytical method to quantify MPs in organic amendments that could support new legislation.

Authentication of recycled plastic content in water bottles using volatile fingerprint and chemometrics.

The environment is threatened by the continuously increasing volume of plastic residue. Plastic recycling is an interesting alternative to mitigate this problem. However, recycled plastic products may have pollutants from their recycling process, collecting system and/or previous life which may hurt consumers health, thus making it key to authenticate and characterize recycled materials. An innovative non-targeted methodology by means of static headspace gas chromatography-mass spectrometry (SHS-GC-MS) has been developed to measure the volatile organic profile of virgin polyethylene terephthalate (PET) and with diverse content of recycled PET samples. A home-made MS database, with 161 organic compounds characteristics from plastic materials based on the literature, was made. Seventeen of those compounds were found in the studied samples and identified by matching their MS spectra with MS database libraries. These compounds are mainly aldehydes (pentanal, hexanal, heptanal, octanal, nonanal and decanal), and benzene derivatives (styrene, p-xylene, benzaldehyde, methylbenzene, and 1,2-dichlorobenzene) which we found to be the common in the samples of recycled PET. The combination of the dataset consisting in the peak area of the detected species by SHS-GC-MS and the use of chemometrics shown to be a valuable methodology for the discrimination between virgin PET samples and those with different recycled PET content based on their volatile profile. In addition, a novel strategy applying a statistical model based on partial least squares (PLS) regression was proposed, for the first time, to quantify the recycled plastic content in the PET samples.

Non-targeted analysis by DLLME-GC-MS for the monitoring of pollutants in the Mar Menor lagoon.

Non-targeted analysis for the monitoring of organic pollutants resulting from agricultural and industrial practices, plastics and pharmaceutical products of seawater from the Mar Menor lagoon (SE Spain) is proposed using dispersive liquid-liquid microextraction (DLLME) and gas chromatography-mass spectrometry (GC-MS). Initially, a home-made MS database including 118 environmental organic pollutants, whose presence in different ecosystems has already been reported, was created. The analytical method was applied for the analysis of 42 samples and a total of 18 pollutants were detected and identified. Samples were obtained from different sites around the Mar Menor in three sampling campaigns, enabling the assessment of impact of rain on the input of the detected chemicals and their distribution. In addition, this methodology was validated using a standard mixture containing 54 of the environmental pollutants included in the database, allowing the quantification of the 9 of the identified compounds (dibutyl phthalate, diisobutyl phthalate, diethyl phthalate, bis(2-ethylhexyl) phthalate, anthracene, 2-methylnaphthalene, hexachlorocyclopentadiene, bis(2-ethylhexyl) adipate and oleamide) with concentration between 3 and 271 µg L-1.

Assessment of anthropogenic pollution by monitoring occurrence and distribution of chemicals in the river Liffey in Dublin.

This paper evaluates for the first time the spatial distribution of a wide group of organic (phthalates, nitro, aliphatic, halogen, aromatic, phenol and amino compounds) and inorganic pollutants along the Liffey river in Dublin city. The work takes into account the effect of short-term weather conditions on the occurrence of these contaminants. The results showed that rainfall conditions affect the levels of pollutants along the river in the days following a rainfall event. In addition, the tributaries entering the river Liffey were not found to impact its water quality. In relation to organic pollutants, 2,4,6-trichlorophenol, 2-nitrophenol and phthalate compounds were found in many water samples between concentrations of 0.21 and 2.17 µg L-1. On the other hand, dimethyl phthalate was present in certain samples at levels around 100 µg L-1. The levels of these contaminants in the river were lower than the toxicity values reported in the literature. Regarding inorganic pollutants, nitrates were detected from 0.59 to 6.81 mg L-1 increasing from upstream to downstream. Based on the chemical nature and applications of detected pollutants, the river contamination can be mainly related to agricultural, industrial activities as well as diffuse urban contributions. These vary with location within a short distance and have the potential to impact aquatic biodiversity as the chemical composition changes with rainfall events.

Targeted and untargeted gas chromatography-mass spectrometry analysis of honey samples for determination of migrants from plastic packages.

Plastic food packages usually contain additives which may migrate from the package into the food and then be ingested by the consumer, representing a risk for their health. In this study, targeted and untargeted analysis by gas chromatography-mass spectrometry (GC-MS) is proposed to monitor any contaminants of this type in honey. The application of dispersive liquid-liquid microextraction (DLLME) as a preconcentration technique allowed very low detection limits to be reached for all the substances. Fifteen target compounds, including styrene, phthalates, fatty acids, alkylphenols and bisphenol A, were quantified. Untargeted analyses were also carried out, allowing other migrants in the honey samples to be identified, such as two phthalates, four acids, three esters, one aldehyde, one hydrocarbon and two alkyl phenol compounds. The proposed method was seen to be a useful approach for the quantification and identification of potential migrants from plastics in challenging samples such as honey.

An overview of microplastics characterization by thermal analysis.

Microplastics may be present in the environment as primary microplastics (manufactured) or secondary microplastics (result of the continuous degradation of larger plastic pieces into smaller fragments due to environmental, physicochemical and biotic factors). To fully understand the dynamics of microplastic particles and their environmental effects, harmonized, automated, cheap, rapid and reliable methodologies for sampling, extraction and characterization of microplastic need to be developed. This review focuses on the potential of thermal analytical techniques for microplastics characterization and highlights some of the new trends in this area.

Comparison of two derivatization reagents for the simultaneous determination of organolead and organomanganese compounds using solid-phase microextraction followed by gas chromatography with atomic emission detection.

Two procedures for the simultaneous determination of organolead (tetraethyllead, triethyllead and trimethyllead) and organomanganese compounds (cyclopentadienyl manganese tricarbonyl (CMT) and methylcyclopentadienyl manganese tricarbonyl (MMT)) are studied. Both procedures involve sample preconcentration by solid-phase microextraction and capillary gas chromatography coupled to atomic emission detection, the main difference being the derivatizing agent used for the ionic alkylated lead species: sodium tetrapropylborate (NaBPr(4)) and sodium tetraphenylborate (NaBPh(4)). The parameters affecting the derivatization and preconcentration steps, chromatographic separation as well as detection of the compounds were optimized. Higher sensitivity was attained for all compounds with the method involving propylation derivatization. In this case, detection limits ranged between 0.04 and 0.1 ng L(-1), depending on the compound. Detection limits of between 0.1 and 24.5 ng L(-1) were obtained, when using phenylation derivatization. A low CMT concentration was found in one of the seawater samples analyzed.

Evaluation of dispersive liquid-liquid microextraction for the simultaneous determination of chlorophenols and haloanisoles in wines and cork stoppers using gas chromatography-mass spectrometry.

Dispersive liquid-liquid microextraction (DLLME) coupled with gas chromatography-mass spectrometry (GC-MS) was evaluated for the simultaneous determination of five chlorophenols and seven haloanisoles in wines and cork stoppers. Parameters, such as the nature and volume of the extracting and disperser solvents, extraction time, salt addition, centrifugation time and sample volume or mass, affecting the DLLME were carefully optimized to extract and preconcentrate chlorophenols, in the form of their acetylated derivatives, and haloanisoles. In this extraction method, 1mL of acetone (disperser solvent) containing 30µL of carbon tetrachloride (extraction solvent) was rapidly injected by a syringe into 5mL of sample solution containing 200µL of acetic anhydride (derivatizing reagent) and 0.5mL of phosphate buffer solution, thereby forming a cloudy solution. After extraction, phase separation was performed by centrifugation, and a volume of 4µL of the sedimented phase was analyzed by GC-MS. The wine samples were directly used for the DLLME extraction (red wines required a 1:1 dilution with water). For cork samples, the target analytes were first extracted with pentane, the solvent was evaporated and the residue reconstituted with acetone before DLLME. The use of an internal standard (2,4-dibromoanisole) notably improved the repeatability of the procedure. Under the optimized conditions, detection limits ranged from 0.004 to 0.108ngmL(-1) in wine samples (24-220pgg(-1) in corks), depending on the compound and the sample analyzed. The enrichment factors for haloanisoles were in the 380-700-fold range.

Determination of dimethylselenide and dimethyldiselenide in milk and milk by-products by solid-phase microextraction and gas chromatography with atomic emission detection.

A method based on solid-phase microextraction (SPME) followed by gas chromatography with microwave-induced plasma atomic emission detection for determining dimethylselenide (DMSe) and dimethyldiselenide (DMDSe) in milk and milk by-products is proposed. Parameters affecting the SPME, such as sample volume or mass, ionic strength, adsorption and desorption times and temperatures were optimized in the headspace mode. The matrix effect was evaluated for the different samples studied, concluding that standard additions calibration was required for quantification purposes. The detection limits ranged from 70 to 110 pg mL(-1) for DMSe and from 80 to 400 pg mL(-1) for DMDSe, depending on the sample under analysis. None of the twenty-three samples analyzed contained the studied compounds at concentrations above the corresponding detection limits.

Headspace solid-phase microextraction for the determination of volatile organic sulphur and selenium compounds in beers, wines and spirits using gas chromatography and atomic emission detection.

A rapid and solvent-free method for the determination of eight volatile organic sulphur and two selenium compounds in different beverage samples using headspace solid-phase microextraction and gas chromatography with atomic emission detection has been developed. The bonded carboxen/polydimethylsiloxane fiber was the most suitable for preconcentrating the analytes from the headspace of the sample solution. Volumes of 20 mL of undiluted beer were used while, in the case of wines and spirits, sample:water ratios of 5:15 and 2:18, respectively, were used, in order to obtain the maximum sensitivity. Quantitation was carried out by using synthetic matrices of beer and wine, and a spiked sample for spirits, and using ethyl methyl sulphide and isopropyl disulphide as internal standards. Detection limits ranged from 8 ng L(-1) to 40 ng mL(-1), depending on the compound and the beverage sample analyzed, with a fiber time exposure of 20 min at ambient temperature. The optimized method was successfully applied to different samples, some of the studied compounds being detected at concentration levels in the 0.04-152 ng mL(-1) range.

Solid-phase microextraction for the determination of haloanisoles in wines and other alcoholic beverages using gas chromatography and atomic emission detection.

UNLABELLED: A headspace solid-phase microextraction (HS-SPME) method for the determination of 12 haloanisoles in wine and spirit samples using gas chromatography with atomic emission detection (GC-AED) was developed. The different factors affecting the efficiency of the extraction were carefully optimized. The divinylbenzene/Carboxen/polydimethylsiloxane (DVB/CAR/PDMS) fiber was the most suitable for preconcentrating the analytes from the headspace of the sample solution. SAMPLE: water dilutions of 3:4 and 1:6 for wines and spirits, respectively, and the use of a mixed bromochloroanisole compound as internal standard allowed sample quantification against external standards prepared in the presence of 5% (v/v) ethanol. Detection limits ranged from 1.2 to 18.5ngL(-1), depending on the compound and the sample analyzed, with a fiber time exposure of 60min at 75 degrees C. The optimized method was successfully applied to different samples, and several of the studied haloanisoles were detected at concentration levels ranging from 10.3ngL(-1) to 1.14ngmL(-1).

Solid-phase microextraction combined with gas chromatography and atomic emission detection for the determination of cyclopentadienylmanganese tricarbonyl and (methylcyclopentadienyl)manganese tricarbonyl in soils and seawaters.

A method based on solid-phase microextraction with capillary gas chromatography and microwave-induced plasma atomic emission detection (SPME-GC-MIP-AED) for the determination of cyclopentadienylmanganese tricarbonyl (CMT) and its methyl derivative, (methylcyclopentadienyl)manganese tricarbonyl (MMT) in seawaters and soils was optimized and evaluated. The solvent-free preconcentration step was carried out in the headspace (HS) mode. Element-specific detection and quantification was carried out by monitoring the manganese (259 nm) emission line. A matrix effect was found for the soil samples investigated, so that standard additions were required for their quantification. On the other hand seawaters were analyzed by applying direct calibration against aqueous standards. Detection limits of 13 and 15 pg Mn L(-1) were obtained for CMT and MMT, respectively, in seawaters, and 0.62 and 0.65 pg Mn g(-1), respectively, for the soil samples. The method permitted recoveries of 76-113%, depending on the compound and the sample analyzed, confirming the reliability of the procedure and its suitability for routine monitoring purposes.

Comparison of two derivatizing agents for the simultaneous determination of selenite and organoselenium species by gas chromatography and atomic emission detection after preconcentration using solid-phase microextraction.

Two methods for the simultaneous determination of selenite and two organoselenium compounds, dimethylselenide (DMSe) and dimethyldiselenide (DMDSe), are proposed. Both methods involve sample preconcentration by solid-phase microextraction (SPME) and capillary gas chromatography coupled to atomic emission detection (GC-AED). The main difference between the methods is the derivatizing agent used to complex the inorganic species: sodium tetraethylborate and 4,5-dichloro-1,2-phenylenediamine. The parameters affecting the derivatization and preconcentration steps, chromatographic separation as well as detection of the compounds were optimized. Direct immersion (DI) mode and a relatively long extraction time were selected for the method involving the formation of the piazselenol complex, better sensitivity being achieved for the three analytes under study. In this case, detection limits ranged between 3 and 25 ng L(-1), depending on the compound. Headspace mode (HS) and extraction times of 20 min were selected for the method involving tetraalkylborate, and detection limits of between 7.3 and 55 ng L(-1) were obtained. DMSe and Se(IV) were found in several of the water samples analyzed at concentrations of 0.07-1.0 ng mL(-1).

A sensitive solid-phase microextraction/gas chromatography-based procedure for determining pentachlorophenol in food.

A new method for the determination of pentachlorophenol (PCP) in different foods was developed using capillary gas chromatography (GC) and microwave induced-plasma atomic emission spectrometry (MIP-AED). The analyte is first derivatized and then extracted and pre-concentrated by solid-phase microextraction (SPME) in headspace (HS) mode. A clear matrix effect was found for the different samples investigated, so that standard addition was required for quantification. Detection limits of 0.03-6.0 ng g(-1) were obtained, depending on the sample analysed. The method gave recoveries of 81-109% from spiked samples. Concentration levels of PCP ranged from 0.3 to 1.5 ng g(-1) were found in honey, but no PCP was detected in other samples.

Pesticide analysis in herbal infusions by solid-phase microextraction and gas chromatography with atomic emission detection.

A direct immersion solid-phase microextraction (SPME) procedure was used in combination with capillary gas chromatography with atomic emission detection (GC-AED) for the determination of 10 pesticides (organochlorines, organophosphorus compounds and pyrethrins) in herbal and tea infusions. Ionic strength, sample dilution and time and temperature of the absorption and desorption stages were some of the parameters investigated in order to select the optimum conditions for SPME with a 100mum PDMS fiber-coating. Element-specific detection and quantification was carried out by monitoring the chlorine (479nm) and bromine (478nm) emission lines, which provided nearly specific chromatograms. Calibration was carried out by using a spiked sample infusion. The detection limits varied between 11.9ngml(-1) for deltamethrin and 0.03ngml(-1) for p,p'-DDE and p,p'-DDD. The recoveries ranged from 73.5% for deltamethrin to 108.3% for p,p'-DDT in a spiked white tea infusion. Two of the eight samples analyzed contained low levels of some the pesticides considered.

Evaluation of solid-phase microextraction conditions for the determination of chlorophenols in honey samples using gas chromatography.

A rapid and solvent-free method for the determination of nine chlorophenol (CP) compounds in honey samples using headspace solid-phase microextraction (HS-SPME) and gas chromatography with atomic emission detection (GC-AED) is developed. The different factors affecting the efficiency of the extraction and derivatization steps were carefully optimized. The polydimethylsiloxane-divinylbenzene (PDMS/DVB) fiber was the most suitable for preconcentrating the analytes from the headspace of an aqueous solution containing the dissolved honey samples where the chlorophenols had been submitted to acetylation. When the matrix effect was evaluated for different samples, it was concluded that standard addition calibration was required for quantification purposes. Detection limits roughly ranged from 0.1 to 2.4 ng g(-1), depending on the compound and the honey sample analyzed, with a fiber time exposure of only 15 min at 75 degrees C. The optimized method was successfully applied to different samples, some of the studied chlorophenols being detected in some of the analyzed honeys at concentration levels 0.6-9.4 ng g(-1).