Extraction Thermal Desorption Gas Chromatography Mass Spectrometry Research Articles

Regression analysis for the determination of microplastics in sediments using differential scanning calorimetry.

This research addresses the growing need for fast and cost-efficient methods for microplastic (MP) analysis. We present a thermo-analytical method that enables the identification and quantification of different polymer types in sediment and sand composite samples based on their phase transition behavior. Differential scanning calorimetry (DSC) was performed, and the results were evaluated by using different regression models. The melting and crystallization enthalpies or the change in heat capacity at the glass transition point were measured as regression analysis data. Ten milligrams of sea sand was spiked with 0.05 to 1.5mg of microplastic particles (size: 100 to 200µm) of the semi-crystalline polymers LD-PE, HD-PE, PP, PA6, and PET, and the amorphous polymers PS and PVC. The results showed that a two-factorial regression enabled the unambiguous identification and robust quantification of different polymer types. The limits of quantification were 0.13 to 0.33mg and 0.40 to 1.84mg per measurement for semi-crystalline and amorphous polymers, respectively. Moreover, DSC is robust with regard to natural organic matrices and allows the fast and non-destructive analysis of microplastic within the analytical limits. Hence, DSC could expand the range of analytical methods for microplastics and compete with perturbation-prone chemical analyses such as thermal extraction-desorption gas chromatography-mass spectrometry or spectroscopic methods. Further work should focus on potential changes in phase transition behavior in more complex matrices and the application of DSC for MP analysis in environmental samples.

A promising approach to monitor microplastic masses in composts

Inputs of plastic impurities into the environment via the application of fertilizers are regulated in Germany and the EU by means of ordinances. Robust and fast analytical methods are the basis of legal regulations. Currently, only macro- and large microplastic contents (>1 mm) are measured. Microplastics (1–1,000 µm), are not yet monitored. Thermal analytical methods are suitable for this purpose, which can determine the mass content and can also be operated fully automatically in routine mode. Thermal extraction desorption-gas chromatography/mass spectrometry (TED-GC/MS) allows the identification of polymers and the determination of mass contents in solid samples from natural environments. In accordance with the German or European Commission (EC) Fertiliser Ordinance, composting plants should be monitored for microplastic particles with this method in the future. In this context a compost plant was sampled. At the end of the rotting process, the compost was sieved and separated in a coarse (>1 mm) and a fine fraction (<1 mm). The fine fraction was processed using density separation comparing NaCl and NaI as possible salt alternative and screened for microplastic masses by TED-GC/MS with additional validation and quality assurance experiments. With TED-GC/MS total microplastics mass contents of 1.1–3.0 μg/mg in finished compost could be detected with polyethylene mainly. What differs much to the total mass of plastics in the coarse fraction with up to 60 μg/mg, which were visually searched, identified via ATR-FTIR and gravimetrically weighted.

Determination of atmospherically deposited microplastics in moss: Method development and performance evaluation

The investigation of atmospheric microplastic pollution is a rising topic within microplastic research. However, sampling strategies concerning atmospheric microplastics are not standardized yet and strongly depend on the scientific objectives investigated. A few research groups are currently focused on determining atmospherically deposited microplastics in moss, as it can be a biomonitoring system for other atmospheric pollutants such as heavy metals, nitrogen, and persistent organic components. In this context, and for atmospheric microplastics in general, almost all examinations focus on determining microplastic numbers and shapes, while polymer masses are barely investigated. However, particle- and mass-based information are needed to assess the fate of atmospherically transported microplastics in the environment. For this purpose, this study shows the development and evaluation of a new sample preparation method for determining microplastics in moss for both analytical approaches using thermal extraction desorption-gas chromatography-mass spectrometry (TED-GC-MS) and Raman microspectroscopy (µRaman). Further, this newly developed microplastics/moss separation method (µPEEL) was compared to oxidative digestion using Fenton's reagent, usually used as a sample preparation method for organic-rich samples and moss. The method comparison was performed concerning green analytical chemistry (GAC) and its respective method functionality. The greenness was assessed using the software tool AGREEprep, which covers ten comprehensive aspects of GAC. Both methods’ functionality was assessed regarding observable matrix interferences and the data quality achieved. It is demonstrated that µPEEL benefits GAC and method functionality since harmful chemicals can be avoided, matrix interferences can be minimized, and the separation quality is increased.

Efficient and sustainable microplastics analysis for environmental samples using flotation for sample pre-treatment

• Separation of microplastics from soil with water and air only • Robust, efficient and green sample preparation with a high separation quality • Investigations were performed by using TED-GC-MS and µRaman • Assessment of sample preparation approaches regarding green analytical chemistry Microplastics analysis in solid environmental samples like sediments and soils requires complex preparation steps to eliminate interfering matrix components. This is often combined with the use of highly concentrated, expensive, and environmentally harmful chemicals. These sample preparation methods can be very time-consuming. Hence, with regard to green analytical chemistry, reduction of emissions and hazards, these sample preparation methods should be modified or avoided, and more environmentally friendly methods should be developed. The characterization and evaluation of the optimized hydrophobicity-water/air-based enrichment cell for microplastics (µSEP) are presented in this study. The separation mechanism of µSEP is based on the hydrophobic adhesion of microplastic on finely dispersed upstreaming air bubbles, serving as a sustainable and practical microplastic sample preparation method. The separation mechanism requires only water and air to considerably reduce the matrix for microplastic analysis. Using soil samples as an example, the applicability of the µSEP sample preparation method for the analysis of microplastics by Raman microspectroscopy (µRaman) and thermal extraction-desorption gas chromatography-mass spectrometry (TED-GC-MS) is demonstrated. Within a sample preparation time of 60 minutes, for polyethylene terephthalate (PET), an average recovery of 77% ± 11%, for polystyrene (PS), 42% ± 11%, and for polypropylene (PP) 65% ± 12% was determined. Furthermore, this study evaluates µSEP and other sample preparation methods regarding their ecotoxicological impact based on the recently released software tool AGREEprep. This tool considers ten individual criteria to cover influencing factors of green analytical chemistry.

Microplastics’ analysis in water: Easy handling of samples by a new Thermal Extraction Desorption-Gas Chromatography-Mass Spectrometry (TED-GC/MS) methodology

Thermal Extraction-Desorption (TED) using a thermobalance coupled to a gas chromatograph (GC) with mass spectrometer (MS) detector is an extended method for polymers identification in complex matrixes. A new TED-GC/MS method for microplastics identification is developed in this study, where the whole filter with solids collected from water is thermal treated in a furnace, instead of using a small portion in a Thermogravimetric analysis (TGA) device, avoiding sample handling. Pyrolyzing the whole filter in a tubular furnace has advantages with respect to the standard procedure of using a TGA with a small crucible in TED-GC/MS.The main advantage is the easy manipulation of the sample, since the filter does not have to be manipulated to extract the sample or cut some portions, avoiding sample losses during handling and ensuring that inhomogeneity on the filter surface is not a problem.Furthermore, there are no limitations on the weight of the sample beyond the adsorbent's ability to trap decomposition compounds without becoming saturated, so high intensity signals can be obtained in order to avoid confuse signals with noise, false negatives or values so close of the quantification limit.

Determination of tire wear markers in soil samples and their distribution in a roadside soil

Tire wear (TW) constitutes a significant source of microplastic in terrestrial ecosystems. It is known that particles emitted by roads can have an effect up to 100 m into adjacent areas. Here, we apply for the first-time thermal extraction desorption gas chromatography-mass spectrometry (TED-GC/MS) to determine TW in soil samples by detection of thermal decomposition products of styrene-butadiene rubber (SBR), without additional enrichment. Additionally, zinc contents were determined as an elemental marker for TW. Mixed soil samples were taken along three transects along a German motorway in 0.3, 2.0, and 5.0 m distance from the road. Sampling depths were 0–2, 2–5, 5–10, and 10–20 cm. Four fine fractions, 1 000–500, 500–100, 100–50, and <50 μm, were analyzed.TW contents based on SBR ranged from 155 to 15 898 mg kg−1. TW contents based on zinc were between 413 and 44 812 mg kg−1. Comparison of individual values of SBR and zinc reveals SBR as a more specific marker. Results confirm that most TW ends up in the topsoil within a 2 m distance.The sampling strategy resulted in representative data for a larger area. Standard deviations of quadruple TED-GC/MS determination of SBR were <10% for all grain size fractions. TED-GC/MS is a suitable analytical tool for determining TW in soil samples without the use of toxic chemicals, enrichment, or special sample preparation.

Microplastics’ Analysis in Water: Easy Handling of Samples by a New Thermal Extraction Desorption-Gas Chromatography-Mass Spectrometry (Ted-Gc/Ms) Methodology

Microplastics’ Analysis in Water: Easy Handling of Samples by a New Thermal Extraction Desorption-Gas Chromatography-Mass Spectrometry (Ted-Gc/Ms) Methodology

Microplastics’ Analysis in Water: Easy Handling of Samples by a New Thermal Extraction Desorption-Gas Chromatography-Mass Spectrometry (Ted-Gc/Ms) Methodology

Microplastics’ Analysis in Water: Easy Handling of Samples by a New Thermal Extraction Desorption-Gas Chromatography-Mass Spectrometry (Ted-Gc/Ms) Methodology

Evaluation of thermoanalytical methods equipped with evolved gas analysis for the detection of microplastic in environmental samples

Microplastic particles are currently detected in almost all environmental compartments. The results of detection vary widely, as a multitude of very different methods are used with very different requirements for analytical validity.In this work four thermoanalytical methods are compared and their advantages and limitations are discussed. One of them is thermal extraction-desorption gas chromatography mass spectrometry (TED-GC/MS), an analysis method for microplastic detection that has become established in recent years. In addition, thermogravimetric analysis coupled with Fourier-transform infrared spectroscopy (TGA-FTIR) and mass spectrometry (TGA-MS) were applied, two methods that are less common in this field but are still used in other research areas. Finally, microscale combustion calorimeter (MCC) was applied, a method not yet used for microplastic detection.The presented results are taken from a recently published interlaboratory comparison test by Becker et al. (2020). Here a reference material consisting of suspended matter and specified added polymer masses was examined, and only the results of the recoveries were presented. In the present paper, however, the results for the individual polymers are discussed in detail and individual perspectives for all instruments are shown.It was found that TED-GC/MS is the most suitable method for samples with unknown matrix and unknown, variable kinds and contents of microplastic. TGA-FTIR is a robust method for samples with known matrix and with defined kinds of microplastic. TGA-MS may offer a solution for the detection of PVC particles in the future. MCC can be used as a very fast and simple screening method for the identification of a potential microplastic load of standard polymers in unknown samples.

Characterization of tire and road wear particles from road runoff indicates highly dynamic particle properties

Tire and road wear particles (TRWPs) are heteroagglomerates of tire rubber and other particles deposited on the road surface and one of the main contributors to non-exhaust emissions of automobile traffic. In this study, samples from road environments were analyzed for their TRWP contents and concentrations of eight organic tire constituents. TRWP concentrations were determined by quantifying Zn in the density fraction <1.9 g/cm³ and by thermal extraction desorption-gas chromatography-mass spectrometry (TED-GC/MS) and the concentrations ranged from 3.7 to 480 mg TRWP/g. Strong and statistically significant correlations with TRWPs were found for 2-hydroxybenzothiazole and 2-aminobenzothiazole, indicating that these substances may be suitable markers of TRWPs. The mass distribution of TRWPs in road dust suggests that the main mass fraction formed on roads consists of coarse particles (>100 µm). Data for a sedimentation basin indicate that the fine fraction (<50 µm) is preferentially transported by road runoff into receiving waters. The size distribution and density data of TRWP gathered by three different quantitation approaches also suggest that aging of TRWPs leads to changes in their particle density. An improved understanding of the dynamics of TRWP properties is essential to assess the distribution and dissipation of this contaminant of emerging concern in the environment.

Microplastic analysis using chemical extraction followed by LC-UV analysis: a straightforward approach to determine PET content in environmental samples

BackgroundThe ubiquitous occurrence of microplastic particles in marine and aquatic ecosystems was intensively investigated in the past decade. However, we know less about the presence, fate, and input paths of microplastic in terrestrial ecosystems. A possible entry path for microplastic into terrestrial ecosystems is the agricultural application of sewage sludge and solid bio-waste as fertilizers. Microplastic contained in sewage sludge also includes polyethylene terephthalate (PET), which could originate as fiber from textile products or as a fragment from packaging products (foils, bottles, etc.). Information about microplastic content in such environmental samples is limited yet, as most of the used analytical methods are very time-consuming, regarding sample preparation and detection, require sophisticated analytical tools and eventually need high user knowledge.ResultsHere, we present a simple, specific tool for the analysis of PET microplastic particles based on alkaline extraction of PET from the environmental matrix and subsequent determination of the monomers, terephthalic acid, using liquid chromatography with UV detection (LC-UV). The applicability of the method is shown for different types of PET in several soil-related, terrestrial environmental samples, e.g., soil, sediment, compost, fermentation residues, but also sewage sludge, suspended particles from urban water management systems, and indoor dust. Recoveries for model samples are between 94.5 and 107.1%. Limit of determination and limit of quantification are absolute masses of 0.031 and 0.121 mg PET, respectively. In order to verify the measured mass contents of the environmental samples, a method comparison with thermal extraction-desorption-gas chromatography–mass spectrometry (TED-GC/MS) was conducted. Both methods deliver similar results and corroborated each other. PET mass contents in environmental samples range from values below LOQ in agriculture soil up to 57,000 mg kg−1 in dust samples.ConclusionsWe demonstrate the potential of an integral method based on chemical extraction for the determination of PET mass contents in solid environmental samples. The method was successfully applied to various matrices and may serve as an analytical tool for further investigations of PET-based microplastic in terrestrial ecosystems.

Development and testing of a fractionated filtration for sampling of microplastics in water

A harmonization of sampling, sample preparation and detection is pivotal in order to obtain comparable data on microplastics (MP) in the environment. This paper develops and proposes a suitable sampling concept for waterbodies that considers different plastic specific properties and influencing factors in the environment.Both artificial water including defined MP fractions and the discharge of a wastewater treatment plant were used to verify the derived sampling procedure, sample preparation and the subsequent analysis of MP using thermal extraction-desorption gas chromatography - mass spectrometry (TED-GC-MS).A major finding of this paper is that an application of various particle size classes greatly improves the practical handling of the sampling equipment. Size classes also enable the TED-GC-MS to provide any data on the MP size distribution, a substantial sampling property affecting both the necessary sampling volume and the optimal sampling depth.In the artificial water with defined MP fractions, the recovery rates ranged from 80 to 110%, depending on the different MP types and MP size classes. In the treated wastewater, we found both polyethylene and polystyrene in different size classes and quantities.

Comparison of different methods for MP detection: What can we learn from them, and why asking the right question before measurements matters?

In recent years, an increasing trend towards investigating and monitoring the contamination of the environment by microplastics (MP) (plastic pieces < 5 mm) has been observed worldwide. Nonetheless, a reliable methodology that would facilitate and automate the monitoring of MP is still lacking. With the goal of selecting practical and standardized methods, and considering the challenges in microplastics detection, we present here a critical evaluation of two vibrational spectroscopies, Raman and Fourier transform infrared (FTIR) spectroscopy, and two extraction methods: thermal extraction desorption gas chromatography mass spectrometry (TED-GC-MS) and liquid extraction with subsequent size exclusion chromatography (SEC) using a soil with known contents of PE, PP, PS and PET as reference material. The obtained results were compared in terms of measurement time, technique handling, detection limits and requirements for sample preparation. The results showed that in designing and selecting the right methodology, the scientific question that determines what needs to be understood is significant, and should be considered carefully prior to analysis. Depending on whether the object of interest is quantification of the MP particles in the sample, or merely a quick estimate of sample contamination with plastics, the appropriate method must be selected. To obtain overall information about MP in environmental samples, the combination of several parallel approaches should be considered.

Harmonized internal quality aspects of a multi-residue method for determination of forty-six semivolatile compounds in water by stir-bar-sorptive extraction–thermal desorption gas chromatography–mass spectrometry

Three main aspects of internal quality-internal method validation, internal quality control (IQC), and sample result uncertainty-have been established for a multi-residue method for determination of 46 organic micropollutants (pesticides and polycyclic aromatic hydrocarbons) in water by stir-bar-sorptive extraction (SBSE) and thermal desorption (TD) coupled to capillary gas chromatography-mass spectrometry (GC-MS). From data obtained with increasing time, the process mean and standard deviation were used to harmonize the internal quality statistics. The relationship between these statistics and the hydrophobicity of the compounds was evaluated.