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Separations (ISSN 2297-8739; CODEN: SEPAF2) (formerly Chromatography - ISSN 2227-9075, CODEN: CHROBV) is an international, scientific, peer-reviewed, open access journal published quarterly online by MDPI:
- Open Access - free for readers, with article processing charges (APC) paid by authors or their institutions.
- High visibility: Indexed in the Emerging Sources Citation Index (ESCI) - Web of Science.
- Rapid publication: manuscripts are peer-reviewed and a first decision provided to authors approximately 23 days after submission; acceptance to publication is undertaken in 12.3 days (median values for papers published in the first six months of 2018).
- Recognition of reviewers: reviewers who provide timely, thorough peer-review reports receive vouchers entitling them to a discount on the APC of their next publication in any MDPI journal, in appreciation of the work done.
Latest Articles
Modern Instrumental Limits of Identification of Ignitable Liquids in Forensic Fire Debris Analysis
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Separations 2018, 5(4), 58; https://doi.org/10.3390/separations5040058 - 10 December 2018
Abstract
Forensic fire debris analysis is an important part of fire investigation, and gas chromatography–mass spectrometry (GC-MS) is the accepted standard for detection of ignitable liquids in fire debris. While GC-MS is the dominant technique, comprehensive two-dimensional gas chromatography–mass spectrometry (GC×GC-MS) is gaining popularity.
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Forensic fire debris analysis is an important part of fire investigation, and gas chromatography–mass spectrometry (GC-MS) is the accepted standard for detection of ignitable liquids in fire debris. While GC-MS is the dominant technique, comprehensive two-dimensional gas chromatography–mass spectrometry (GC×GC-MS) is gaining popularity. Despite the broad use of these techniques, their sensitivities are poorly characterized for petroleum-based ignitable liquids. Accordingly, we explored the limit of identification (LOI) using the protocols currently applied in accredited forensic labs for two 75% evaporated gasolines and a 25% evaporated diesel as both neat samples and in the presence of interfering pyrolysate typical of fire debris. GC-MSD (mass selective detector (MS)), GC-TOF (time-of-flight (MS)), and GC×GC-TOF were evaluated under matched conditions to determine the volume of ignitable liquid required on-column for correct identification by three experienced forensic examiners performing chromatographic interpretation in accordance with ASTM E1618-14. GC-MSD provided LOIs of ~0.6 pL on-column for both neat gasolines, and ~12.5 pL on-column for neat diesel. In the presence of pyrolysate, the gasoline LOIs increased to ~6.2 pL on-column, while diesel could not be correctly identified at the concentrations tested. For the neat dilutions, GC-TOF generally provided 2× better sensitivity over GC-MSD, while GC×GC-TOF generally resulted in 10× better sensitivity over GC-MSD. In the presence of pyrolysate, GC-TOF was generally equivalent to GC-MSD, while GC×GC-TOF continued to show 10× greater sensitivity relative to GC-MSD. Our findings demonstrate the superior sensitivity of GC×GC-TOF and provide an important approach for interlaboratory benchmarking of modern instrumental performance in fire debris analysis.
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Chemometric Characterization of Synthetic Dye Sorption onto Slovakian River Sediments: A Laboratory Batch Experiment
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Separations 2018, 5(4), 57; https://doi.org/10.3390/separations5040057 - 4 December 2018
Abstract
The aim of the work was to characterize the sorption of cationic dyes thioflavine T (ThT) and methylene blue (MB) onto selected Slovakian river sediments using chemometric approaches including principal component analysis (PCA) and cluster analysis (CA). Also, the potential of mentioned multivariate
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The aim of the work was to characterize the sorption of cationic dyes thioflavine T (ThT) and methylene blue (MB) onto selected Slovakian river sediments using chemometric approaches including principal component analysis (PCA) and cluster analysis (CA). Also, the potential of mentioned multivariate analyses for comparison of studied objects (river sediments or river and model waters) as well as in finding relationships between the variables describing the physico-chemical characteristics of studied matrices or waters and sorption/desorption characteristics of matrices for dyes binding under laboratory conditions was evaluated. Parameters describing the physico-chemical characteristics of sediments include: pH, pHzpc, or cation-exchange capacity; and in the case of waters: pH, conductivity, water hardness, content of dissolved solids or presence of organic compounds. From the comparison of dye sorption onto sediments, it was found that sorption of thiazine dye MB was minimally 1.5-times higher than sorption of benzothiazole dye ThT. Sorption capacities Qs reached the maximum values in the case of sediments originated from Dudvah River (MB-Qs = 8.70 ± 0.42 mg g−1; ThT-Qs = 5.03 ± 0.28 mg g−1; ±SD). Obtained results showed that applied methods of multivariate analyses represent a suitable tool for evaluation of sorption/desorption processes of organic xenobiotics binding in sediments.
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Challenges in Determining the Size Distribution of Nanoparticles in Consumer Products by Asymmetric Flow Field-Flow Fractionation Coupled to Inductively Coupled Plasma-Mass Spectrometry: The Example of Al2O3, TiO2, and SiO2 Nanoparticles in Toothpaste
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Separations 2018, 5(4), 56; https://doi.org/10.3390/separations5040056 - 27 November 2018
Abstract
According to the current European regulation on cosmetics, any ingredient present as a nanomaterial should be indicated in the ingredient list. There is a need for analytical methods capable of determining the size of the relevant ingredients and thus assessing if these are
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According to the current European regulation on cosmetics, any ingredient present as a nanomaterial should be indicated in the ingredient list. There is a need for analytical methods capable of determining the size of the relevant ingredients and thus assessing if these are nanomaterials or not. An analytical method based on asymmetric flow field-flow fractionation (AF4) and inductively coupled plasma-mass spectrometry (ICP-MS) was developed to determine the size of particles present in a commercial toothpaste. Multi-angle light scattering (MALS) was used for on-line size determination. The number-based particle size distributions (PSDs) of the particles were retrieved upon mathematical conversion of the mass-based PSDs recovered from the AF4-ICP-MS fractograms. AF4-ICP-MS allowed to separate and detect Al2O3 and TiO2 particles in the toothpaste and to retrieve a correct TiO2 number-based PSD. The potential presence of particles in the lower size range of the Al2O3 mass-based PSD had a strong impact on sizing and nanomaterial classification upon conversion. AF4 coupled with ICP-MS and MALS was found to be a powerful approach for characterization of different particles in a multiple-particle system such as toothpaste. Confirmation of particle size by a secondary method such as single particle ICP-MS or hydrodynamic chromatography was crucial.
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A Low-Cost Approach Using Diatomaceous Earth Biosorbent as Alternative SPME Coating for the Determination of PAHs in Water Samples by GC-MS
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Separations 2018, 5(4), 55; https://doi.org/10.3390/separations5040055 - 20 November 2018
Abstract
In this study, the use of recycled diatomaceous earth as the extraction phase in solid phase microextraction (SPME) technique for the determination of polycyclic aromatic hydrocarbons (PAHs) in river water samples, with separation/detection performed by gas chromatography-mass spectrometry (GC-MS), is proposed. The optimized
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In this study, the use of recycled diatomaceous earth as the extraction phase in solid phase microextraction (SPME) technique for the determination of polycyclic aromatic hydrocarbons (PAHs) in river water samples, with separation/detection performed by gas chromatography-mass spectrometry (GC-MS), is proposed. The optimized extraction conditions are extraction time 70 min at 80 °C with no addition of salt. The limits of quantification were close to 0.5 μg L−1 with RSD values lower than 25% (n = 3). The linear working range was 0.5 μg L−1 to 25 μg L−1 for all analytes. The method was applied to samples collected from the Itajaí River (Santa Catarina, Brazil) and the RSD values for repeatability and reproducibility were lower than 15% and 17%, respectively. The efficiency of the recycled diatomaceous earth fiber was compared with that of commercial fibers and good results were obtained, confirming that this is a promising option to use as the extraction phase in SPME.
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Biosorption and Bioaccumulation Abilities of Actinomycetes/Streptomycetes Isolated from Metal Contaminated Sites
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Separations 2018, 5(4), 54; https://doi.org/10.3390/separations5040054 - 12 November 2018
Abstract
Heavy metal pollution is of great concern. Due to expansion of industrial activities, a large amount of metal is released into the environment, disturbing its fragile balance. Conventional methods of remediation of heavy metal-polluted soil and water are expensive and inefficient. Therefore, new
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Heavy metal pollution is of great concern. Due to expansion of industrial activities, a large amount of metal is released into the environment, disturbing its fragile balance. Conventional methods of remediation of heavy metal-polluted soil and water are expensive and inefficient. Therefore, new techniques are needed to provide environmentally friendly and highly selective remediation. Streptomycetes, with their unique growth characteristics, ability to form spores and mycelia, and relatively rapid colonization of substrates, act as suitable agents for bioremediation of metals and organic compounds in polluted soil and water. A variety of mechanisms could be involved in reduction of metals in the environment, e.g., sorption to exopolymers, precipitation, biosorption and bioaccumulation. Studies performed on biosorption and bioaccumulation potential of streptomycetes could be used as a basis for further development in this field. Streptomycetes are of interest because of their ability to survive in environments contaminated by metals through the production of a wide range of metal ion chelators, such as siderophores, which provide protection from the negative effects of heavy metals or specific uptake for specialized metabolic processes. Many strains also have the equally important characteristic of resistance to high concentrations of heavy metals.
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Evaluation of Lipases from Wild Microbial Strains as Biocatalysts in Biodiesel Production
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Separations 2018, 5(4), 53; https://doi.org/10.3390/separations5040053 - 5 November 2018
Abstract
In this study, the evaluation of the catalytic behavior of several wild bacterial strains in the 1,3-selective ethanolysis of triglycerides with ethanol to produce a new type of biodiesel (Ecodiesel) that integrates glycerol as monoacylglycerols was carried out. The Ecodiesel production not only
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In this study, the evaluation of the catalytic behavior of several wild bacterial strains in the 1,3-selective ethanolysis of triglycerides with ethanol to produce a new type of biodiesel (Ecodiesel) that integrates glycerol as monoacylglycerols was carried out. The Ecodiesel production not only avoids the elimination of glycerol, which is largely generated as a by-product in the biodiesel industry, but also results in an increase in the biofuel yield. The wild microbial strain samples were obtained from several lipophilic organisms. In addition to evaluate the enzymatic extracts, the minimum grade of purification of the strains, necessary to obtain similar results to those attained with commercial lipases was studied. This purification treatment included a dialysis followed by a lyophilization process. Such extracts were directly used as biocatalysts in the transesterification reaction of sunflower oil with ethanol, attaining much better results (yield close to 100%) than those obtained with strains which were not submitted to the purification process (yields lower than 10%). Furthermore, the results here obtained are similar to those obtained with commercial lipases but were achieved under mild conditions and lower reaction time (2 h). In addition, the stability of the enzymatic extracts was corroborated by subsequent reactions, showing no loss of activity. Thus, this study brings to light that enzymatic extracts obtained by a very simple purification process can be economically competitive with the conventional biodiesel production methods.
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Application of Self-Organizing Maps to the Analysis of Ignitable Liquid and Substrate Pyrolysis Samples
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Separations 2018, 5(4), 52; https://doi.org/10.3390/separations5040052 - 31 October 2018
Abstract
Classification of un-weathered ignitable liquids is a problem that is currently addressed by visual pattern recognition under the guidelines of Standard Test Method for Ignitable Liquid Residues in Extracts from Fire Debris Samples by Gas Chromatography-Mass Spectrometry, ASTM E1618-14. This standard method does
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Classification of un-weathered ignitable liquids is a problem that is currently addressed by visual pattern recognition under the guidelines of Standard Test Method for Ignitable Liquid Residues in Extracts from Fire Debris Samples by Gas Chromatography-Mass Spectrometry, ASTM E1618-14. This standard method does not separately address the identification of substrate pyrolysis patterns. This report details the use of a Kohonen self-organizing map coupled with extracted ion spectra to organize ignitable liquids and substrate pyrolysis samples on a two-dimensional map with groupings that correspond to the ASTM-classifications and separate the substrate pyrolysis samples from the ignitable liquids. The component planes give important information regarding the ions from the extracted ion spectra that contribute to the different classes. Some additional insight is gained into grouping of substrate pyrolysis samples based on the nature of the unburned material as a wood or non-wood material. Further subclassification was not apparent from the self-organizing maps (SOM) results.
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Investigation of Hg Content by a Rapid Analytical Technique in Mediterranean Pelagic Fishes
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Separations 2018, 5(4), 51; https://doi.org/10.3390/separations5040051 - 24 October 2018
Abstract
Mercury (Hg) fish and seafood contamination is a global concern and needs worldwide sea investigations in order to protect consumers. The aim of this study was to investigate the Hg concentration by means of a rapid and simple analytical technique with a direct
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Mercury (Hg) fish and seafood contamination is a global concern and needs worldwide sea investigations in order to protect consumers. The aim of this study was to investigate the Hg concentration by means of a rapid and simple analytical technique with a direct Mercury Analyzer (DMA-80) in pelagic fish species, Tetrapturus belone (spearfish), Thunnus thynnus (tuna) and Xiphias gladius (swordfish) caught in the Mediterranean Sea. Hg contents were evaluated also in Salmo salar (salmon) as pelagic fish not belonging to the Mediterranean area. The results obtained were variable, ranging between 0.015–2.562 mg kg−1 for T. thynnus species, 0.477–3.182 mg kg−1 for X. gladius, 0.434–1.730 mg kg−1 for T. belone and 0.004–0.019 mg kg−1 for S. salar, respectively. The total Hg tolerable weekly intake (TWI) and tolerable weekly intake % (TWI%) values according to the European Food Safety Authority (EFSA) were calculated. The results highlighted that the pelagic species caught in the Mediterranean Sea should be constantly monitored due to their high Hg contents as well as their TWI and TWI% with respect to S. salar samples.
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Characterization of the Natural Colloidal TiO2 Background in Soil
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Separations 2018, 5(4), 50; https://doi.org/10.3390/separations5040050 - 20 October 2018
Abstract
An increasing amount of TiO2 engineered nanoparticles (TNP) is released into soils and sediments, increasing the need for dedicated detection methods. Titanium is naturally present in soils at concentrations typically much higher than the estimated concentrations for TNP. Therefore, a precise knowledge
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An increasing amount of TiO2 engineered nanoparticles (TNP) is released into soils and sediments, increasing the need for dedicated detection methods. Titanium is naturally present in soils at concentrations typically much higher than the estimated concentrations for TNP. Therefore, a precise knowledge of this natural background, including the colloidal fraction, is required for developing adapted strategies for detecting TNP. In this study, we characterized the natural colloidal Ti-background by analyzing eight soils with different properties and origins. A combination of X-ray fluorescence analysis and ICP-OES was used for determining the silicate bound fraction, which was a minor fraction for all soils (0–32%). The colloidal fraction obtained by extracting colloids from soil prior to ICP-OES measurements ranged between 0.3% and 7%. Electron microscopy and hydrodynamic chromatography confirmed that Ti in the form of colloids or larger particles was mostly present as TiO2 minerals with a fraction smaller than 100 nm. The size distribution mode of the extracted colloids determined using hydrodynamic chromatography ranged between 80 and 120 nm. The chromatograms suggested a broad size distribution with a significant portion below 100 nm. In addition to these data, we also discuss possible implications of our findings for the method development for detecting TNP in soils.
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Estimating Detection Limits in Chromatography from Calibration Data: Ordinary Least Squares Regression vs. Weighted Least Squares
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Separations 2018, 5(4), 49; https://doi.org/10.3390/separations5040049 - 8 October 2018
Abstract
It is necessary to determine the limit of detection when validating any analytical method. For methods with a linear response, a simple and low labor-consuming procedure is to use the linear regression parameters obtained in the calibration to estimate the blank standard deviation
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It is necessary to determine the limit of detection when validating any analytical method. For methods with a linear response, a simple and low labor-consuming procedure is to use the linear regression parameters obtained in the calibration to estimate the blank standard deviation from the residual standard deviation (sres), or the intercept standard deviation (sb0). In this study, multiple experimental calibrations are evaluated, applying both ordinary and weighted least squares. Moreover, the analyses of replicated blank matrices, spiked at 2–5 times the lowest calculated limit values with the two regression methods, are performed to obtain the standard deviation of the blank. The limits of detection obtained with ordinary least squares, weighted least squares, the signal-to-noise ratio, and replicate blank measurements are then compared. Ordinary least squares, which is the simplest and most commonly applied calibration regression methodology, always overestimate the values of the standard deviations at the lower levels of calibration ranges. As a result, the detection limits are up to one order of magnitude greater than those obtained with the other approaches studied, which all gave similar limits.
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Monolithic Silica Capillary Columns with Improved Retention and Selectivity for Amino Acids
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Separations 2018, 5(4), 48; https://doi.org/10.3390/separations5040048 - 2 October 2018
Abstract
A strategy for the preparation of silica-based monolithic capillary columns (150 × 0.1 mm) with high selectivity to amino acids is presented. The zwitterionic columns were prepared by coating the silica monolith with [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide via 3-(trimethoxysilyl)propyl methacrylate. The columns were evaluated under
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A strategy for the preparation of silica-based monolithic capillary columns (150 × 0.1 mm) with high selectivity to amino acids is presented. The zwitterionic columns were prepared by coating the silica monolith with [2-(methacryloyloxy)ethyl]-dimethyl-(3-sulfopropyl)-ammonium hydroxide via 3-(trimethoxysilyl)propyl methacrylate. The columns were evaluated under isocratic conditions in hydrophilic interaction liquid chromatography. The best separation of amino acids was obtained on the monolithic column prepared by a stepwise modification procedure where the modification step was repeated four times. The mixture of fifteen amino acids was separated within 13 min using the mobile phase consisting of 75% acetonitrile and 25% 5 mmol/L ammonium acetate at pH 4.5.
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Fixed- and Variable-Temperature Kinetic Models to Predict Evaporation of Petroleum Distillates for Fire Debris Applications
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Separations 2018, 5(4), 47; https://doi.org/10.3390/separations5040047 - 25 September 2018
Abstract
Forensic fire debris analysis focuses on the identification of a foreign ignitable liquid in debris collected from the scene of a suspected intentional fire. Chromatograms of the extracted debris are compared to a suitable reference collection containing chromatograms of unevaporated and evaporated ignitable
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Forensic fire debris analysis focuses on the identification of a foreign ignitable liquid in debris collected from the scene of a suspected intentional fire. Chromatograms of the extracted debris are compared to a suitable reference collection containing chromatograms of unevaporated and evaporated ignitable liquids. However, there is no standardized method for the evaporation of ignitable liquids and the process itself can be time consuming, which limits the number of chromatograms of evaporated liquids included in the reference collection. This work describes the development and application of a variable-temperature kinetic model to predict evaporation rate constants and mathematically predict chromatograms corresponding to evaporated ignitable liquids. First-order evaporation rate constants were calculated for 78 selected compounds in diesel, which were used to develop predictive models of evaporation rates. Fixed-temperature models were developed to predict the rate constants at five temperatures (5, 10, 20, 30, 35 °C), yielding a mean absolute percent error (MAPE) of 10.0%. The variable-temperature model was then created from these data by multiple linear regression, yielding a MAPE of 16.4%. The model was applied to generate a reference collection of predicted chromatograms of diesel and kerosene corresponding to a range of evaporation levels. Using the modeled reference collection, successful identification of the liquid and level of evaporation in a test set of chromatograms was demonstrated.
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Developing a Method for the Collection and Analysis of Burnt Remains for the Detection and Identification of Ignitable Liquid Residues Using Body Bags, Dynamic Headspace Sampling, and TD-GC×GC-TOFMS
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Separations 2018, 5(3), 46; https://doi.org/10.3390/separations5030046 - 17 September 2018
Abstract
In cases of suspected arson, a body may be intentionally burnt to cause loss of life, dispose of remains, or conceal identification. A primary focus of a fire investigation, particularly involving human remains, is to establish the cause of the fire; this often
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In cases of suspected arson, a body may be intentionally burnt to cause loss of life, dispose of remains, or conceal identification. A primary focus of a fire investigation, particularly involving human remains, is to establish the cause of the fire; this often includes the forensic analysis of fire debris for the detection of ignitable liquid residues (ILRs). Commercial containers for the collection of fire debris evidence include metal cans, glass jars, and polymer/nylon bags of limited size. This presents a complication in cases where the fire debris consists of an intact, or partially intact, human cadaver. This study proposed the use of a body bag as an alternative sampling container. A method was developed and tested for the collection and analysis of ILRs from burnt porcine remains contained within a body bag using dynamic headspace sampling (using an Easy-VOC™ hand-held manually operated grab-sampler and stainless steel sorbent tubes containing Tenax TA) followed by thermal desorption comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (TD-GC×GC-TOFMS). The results demonstrated that a body bag containing remains burnt with gasoline tested positive for the presence of gasoline, while blank body bag controls and a body bag containing remains burnt without gasoline tested negative. The proposed method permits the collection of headspace samples from burnt remains before the remains are removed from the crime scene, limiting the potential for contamination and the loss of volatiles during transit and storage.
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Sampling Dynamics for Volatile Organic Compounds Using Headspace Solid-Phase Microextraction Arrow for Microbiological Samples
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Separations 2018, 5(3), 45; https://doi.org/10.3390/separations5030045 - 10 September 2018
Abstract
Volatile organic compounds (VOCs) are monitored in numerous fields using several commercially-available sampling options. Sorbent-based sampling techniques, such as solid-phase microextraction (SPME), provide pre-concentration and focusing of VOCs prior to gas chromatography–mass spectrometry (GC–MS) analysis. This study investigated the dynamics of SPME Arrow,
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Volatile organic compounds (VOCs) are monitored in numerous fields using several commercially-available sampling options. Sorbent-based sampling techniques, such as solid-phase microextraction (SPME), provide pre-concentration and focusing of VOCs prior to gas chromatography–mass spectrometry (GC–MS) analysis. This study investigated the dynamics of SPME Arrow, which exhibits an increased sorbent phase volume and improved durability compared to traditional SPME fibers. A volatile reference mixture (VRM) and saturated alkanes mix (SAM) were used to investigate optimal parameters for microbiological VOC profiling in combination with GC–MS analysis. Fiber type, extraction time, desorption time, carryover, and reproducibility were characterized, in addition to a comparison with traditional SPME fibers. The developed method was then applied to longitudinal monitoring of Bacillus subtilis cultures, which represents a ubiquitous microbe in medical, forensic, and agricultural applications. The carbon wide range/polydimethylsiloxane (CWR/PDMS) fiber was found to be optimal for the range of expected VOCs in microbiological profiling, and a statistically significant increase in the majority of VOCs monitored was observed. B. subtilis cultures released a total of 25 VOCs of interest, across three different temporal trend categories (produced, consumed, and equilibrated). This work will assist in providing foundational data for the use of SPME Arrow in future microbiological applications.
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Model Distribution Effects on Likelihood Ratios in Fire Debris Analysis
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Separations 2018, 5(3), 44; https://doi.org/10.3390/separations5030044 - 3 September 2018
Abstract
Computational models for determining the strength of fire debris evidence based on likelihood ratios (LR) were developed and validated against data sets derived from different distributions of ASTM E1618-14 designated ignitable liquid class and substrate pyrolysis contributions using in-silico generated data. The models
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Computational models for determining the strength of fire debris evidence based on likelihood ratios (LR) were developed and validated against data sets derived from different distributions of ASTM E1618-14 designated ignitable liquid class and substrate pyrolysis contributions using in-silico generated data. The models all perform well in cross validation against the distributions used to generate the model. However, a model generated based on data that does not contain representatives from all of the ASTM E1618-14 classes does not perform well in validation with data sets that contain representatives from the missing classes. A quadratic discriminant model based on a balanced data set (ignitable liquid versus substrate pyrolysis), with a uniform distribution of the ASTM E1618-14 classes, performed well (receiver operating characteristic area under the curve of 0.836) when tested against laboratory-developed casework-relevant samples of known ground truth.
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Detection and Characterization of Ignitable Liquid Residues in Forensic Fire Debris Samples by Comprehensive Two-Dimensional Gas Chromatography
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Separations 2018, 5(3), 43; https://doi.org/10.3390/separations5030043 - 27 August 2018
Abstract
This study covers an extensive experimental design that was developed for creating simulated fire debris samples under controlled conditions for the detection and identification of ignitable liquids (IL) residues. This design included 19 different substrates, 45 substrate combinations with and without ignitable liquids,
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This study covers an extensive experimental design that was developed for creating simulated fire debris samples under controlled conditions for the detection and identification of ignitable liquids (IL) residues. This design included 19 different substrates, 45 substrate combinations with and without ignitable liquids, and 45 different ILs from three classes (i.e., white spirit, gasoline, and lamp oil). Chemical analysis was performed with comprehensive two-dimensional gas chromatography coupled to time-of-flight mass spectrometry (GC×GC-TOFMS) for improved separation and compound identification. The enhanced peak capacity offered by GC×GC-TOFMS allowed the use of a target compound list in combination with a simple binary decision model to arrive at quite acceptable results with respect to IL detection (89% true positive and 7% false positive rate) and classification (100% correct white spirit, 79% correct gasoline, and 77% correct lamp oil assignment). Although these results were obtained in a limited set of laboratory controlled fire experiments including only three IL classes, this study confirms the conclusions of other studies that GC×GC-TOFMS can be a powerful tool in the challenging task of forensic fire debris analysis.
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Heterogeneous Catalytic Ozonation of p-Chlorobenzoic Acid in Aqueous Solution by FeMnOOH and PET
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Separations 2018, 5(3), 42; https://doi.org/10.3390/separations5030042 - 20 August 2018
Abstract
The oxidation of p-chlorobenzoic acid (p-CBA), used as a typical-model refractory organic compound, in aqueous solutions during the heterogeneous catalytic ozonation treatment process by applying the hydrophilic tetravalent manganese feroxyhyte (TMFx), as well as modified hydrophobic TMFx and the polyethylene terephthalate (PET) as
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The oxidation of p-chlorobenzoic acid (p-CBA), used as a typical-model refractory organic compound, in aqueous solutions during the heterogeneous catalytic ozonation treatment process by applying the hydrophilic tetravalent manganese feroxyhyte (TMFx), as well as modified hydrophobic TMFx and the polyethylene terephthalate (PET) as solid (powdered) catalysts was examined in this study. TMFx was hydrophobically modified by using trichloromethylsilane (TriClMS) solutions in toluene at the concentration range 10–1000 mg/L. TMFx catalysts were characterized by the application of scanning electron microscopy (SEM), as well as by Brunauer-Emmet-Teller (BET) and surface charge density determinations. TMFx catalyst, which was modified by 50 mg/L trichloromethylsilane (TriClMS) solution (TMFx-50), was found to present the higher adsorption capacity of studied organic compound (250 μg p-CBA/g) when compared with all the other investigated catalysts, which in turn resulted in the higher removal of p-CBA (>99%) by the subsequent application of ozonation, as compared to hydrophilic TMFx (96.5%) and to single ozonation (96%) applications. PET-catalyst concentration in the range 0.5–10 g/L led to almost total removal of p-CBA within 15 min of reaction/oxidation time at pH 7. Conclusively, the experimental results for both catalysts indicated that hydrophobicity and adsorption capacity are crucial steps for the process of heterogeneous catalytic ozonation of refractory organic compounds.
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Application of Headspace Gas Chromatography-Ion Mobility Spectrometry for the Determination of Ignitable Liquids from Fire Debris
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Separations 2018, 5(3), 41; https://doi.org/10.3390/separations5030041 - 13 August 2018
Abstract
A fast and correct identification of ignitable liquid residues in fire debris investigation is of high importance in forensic research. Advanced fast analytical methods combined with chemometric tools are usually applied for these purposes. In the present study, the Headspace Gas Chromatography-Ion Mobility
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A fast and correct identification of ignitable liquid residues in fire debris investigation is of high importance in forensic research. Advanced fast analytical methods combined with chemometric tools are usually applied for these purposes. In the present study, the Headspace Gas Chromatography-Ion Mobility Spectrometry (HS-GC-IMS) combined with chemometrics is proposed as a promising technique for the identification of ignitable liquid residues in fire debris samples. Fire debris samples were created in the laboratory, according to the Destructive Distillation Method for Burning that is provided by the Bureau of Forensic Fire and Explosives. Four different substrates (pine wood, cork, paper, and cotton sheet) and four ignitable liquids of dissimilar composition (gasoline, diesel, ethanol, and paraffin) were used to create the fire debris. The Total Ion Current (TIC) Chromatogram combined with different chemometric tools (hierarchical cluster analysis and linear discriminant analysis) allowed for a full discrimination between samples that were burned with and without ignitable liquids. Additionally, a good identification (95% correct discrimination) for the specific ignitable liquid residues in the samples was achieved. Based on these results, the chromatographic data from HS-GC-IMS have been demonstrated to be very useful for the identification and discrimination of ignitable liquids residues. The main advantages of this approach vs. traditional methodology are that no sample manipulation or solvent is required; it is also faster, cheaper, and easy to use for routine analyses.
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Fabric Phase Sorptive Extraction: Current State of the Art and Future Perspectives
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Separations 2018, 5(3), 40; https://doi.org/10.3390/separations5030040 - 6 August 2018
Abstract
Fabric phase sorptive extraction (FPSE) is a novel and green sample preparation technique introduced in 2014. FPSE utilizes a natural or synthetic permeable and flexible fabric substrate chemically coated with a sol-gel organic-inorganic hybrid sorbent in the form of ultra-thin coating, which leads
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Fabric phase sorptive extraction (FPSE) is a novel and green sample preparation technique introduced in 2014. FPSE utilizes a natural or synthetic permeable and flexible fabric substrate chemically coated with a sol-gel organic-inorganic hybrid sorbent in the form of ultra-thin coating, which leads to a fast and sensitive micro-extraction device. The flexible FPSE requires no modification of samples and allows direct extraction of analytes. Sol-gel sorbent-coated FPSE media possesses high chemical, solvent, and thermal stability due to the strong covalent bonding between the substrate and the sol-gel sorbent. Therefore, any elution solvent can be used in a small volume, which achieves a high pre-concentration factor without requiring any solvent evaporation and sample reconstitution step. Taking into consideration the complexity of the samples and the need of further minimization and automation, some new, alternative modes of the FPSE have also been developed. Therefore, FPSE has attracted the interest of the scientific community that deals with sample pre-treatment and has been successfully applied for the extraction and determination of many analytes in environmental samples as well as in food and biological samples. The objective of the current review is to present and classify the applications of FPSE according to different sample categories and to briefly show the progress, advantages, and the main principles of the proposed technique.
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Effect of Solvents and Extraction Methods on Recovery of Bioactive Compounds from Defatted Gac (Momordica cochinchinensis Spreng.) Seeds
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Separations 2018, 5(3), 39; https://doi.org/10.3390/separations5030039 - 30 July 2018
Abstract
Gac (Momordica cochinchinensis Spreng.) seeds contain bioactive compounds with medicinal properties. This study aimed to determine a suitable solvent and extraction technique for recovery of important compounds, namely, trypsin inhibitors, saponins, and phenolics. The antioxidant capacity and total solids of derived extracts
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Gac (Momordica cochinchinensis Spreng.) seeds contain bioactive compounds with medicinal properties. This study aimed to determine a suitable solvent and extraction technique for recovery of important compounds, namely, trypsin inhibitors, saponins, and phenolics. The antioxidant capacity and total solids of derived extracts were also measured. Water with conventional extraction method gave the highest value of trypsin inhibitor activity (118.45 ± 4.90 mg trypsin g−1) while water-saturated n-butanol and methanol extracts were characterized by their highest content of saponins (40.75 ± 0.31 and 38.80 ± 2.82 mg AE g−1, respectively). Aqueous extract with microwave assistance achieved the highest phenolics (3.18 ± 0.04 mg GAE g−1). As a measure of antioxidant capacity, the 2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid) diammonium salt (ABTS) assay gave highest value to the aqueous microwave extract (23.56 ± 0.82 μmol TE g−1) while the ferric reducing antioxidant power (FRAP) assay gave highest values to water-saturated n-butanol and 70% ethanol extracts (5.25 ± 0.04 and 4.71 ± 0.39 μmol TE g−1, respectively). The total solids value was highest using water with microwave assistance (141.5 g kg−1) while ultrasound treatment did not improve any extractions. Therefore, trypsin inhibitors are suitably recovered using water while water-saturated n-butanol or methanol is for saponins, both using a conventional method. Microwave extraction is suitable for phenolics recovery. These conditions are recommended for an efficient recovery of bioactive compounds from defatted Gac seeds.
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30 October 2018
Institutional Open Access Agreement between Bill and Melinda Gates Foundation and MDPI
Institutional Open Access Agreement between Bill and Melinda Gates Foundation and MDPI
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