Atmospheric pressure gas chromatography-time-of-flight-mass spectrometry (APGC-ToF-MS) for the determination of regulated and emerging contaminants in aqueous samples after stir bar sorptive extraction (SBSE)

This work presents the development, optimization and validation of a multi-residue method for the simultaneous determination of 102 contaminants, including fragrances, UV filters, repellents, endocrine disruptors, biocides, polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and several types of pesticides in aqueous matrices. Water samples were processed using stir bar sorptive extraction (SBSE) after the optimization of several parameters: agitation time, ionic strength, presence of organic modifiers, pH, and volume of the derivatizing agent. Target compounds were extracted from the bars by liquid desorption (LD). Separation, identification and quantification of analytes were carried out by gas chromatography (GC) coupled to time-of-flight (ToF-MS) mass spectrometry. A new ionization source, atmospheric pressure gas chromatography (APGC), was tested. The optimized protocol showed acceptable recovery percentages (50–100%) and limits of detection below 1 ng L−1 for most of the compounds. Occurrence of 21 out of 102 analytes was confirmed in several environmental aquatic matrices, including seawater, sewage effluent, river water and groundwater. Non-target compounds such as organophosphorus flame retardants were also identified in real samples by accurate mass measurement of their molecular ions using GC-APGC–ToF-MS. To the best of our knowledge, this is the first time that this technique has been applied for the analysis of contaminants in aquatic systems. By employing lower energy than the more widely used electron impact ionization (EI), AGPC provides significant advantages over EI for those substances very susceptible to high fragmentation (e.g., fragrances, pyrethroids)

Novel ionization reagent for the measurement of gas-phase ammonia and amines using a stand-alone atmospheric pressure gas chromatography (APGC) source.

RationaleContaminants present in ambient air or in sampling lines can interfere with the target analysis through overlapping peaks or causing a high background. This study presents a positive outcome from the unexpected presence of N-methyl-2-pyrrolidone, released from a PALL HEPA filter, in the analysis of atmospherically relevant gas-phase amines using chemical ionization mass spectrometry.MethodsGas-phase measurements were performed using a triple quadrupole mass spectrometer equipped with a modified atmospheric pressure gas chromatography (APGC) source which allows sampling of the headspace above pure amine standards. Gas-phase N-methyl-2-pyrrolidone (NMP) emitted from a PALL HEPA filter located in the inlet stream served as the ionizing agent.ResultsThis study demonstrates that some alkylamines efficiently form a [NMP + amine+H]+ cluster with NMP upon chemical ionization at atmospheric pressure. The extent of cluster formation depends largely on the proton affinity of the amine compared with that of NMP. Aromatic amines (aniline, pyridine) and diamines (putrescine) were shown not to form cluster ions with NMP.ConclusionsThe use of NMP as an ionizing agent with stand-alone APGC provided high sensitivity for ammonia and the smaller amines. The main advantages, in addition to sensitivity, are direct sampling into the APGC source and avoiding uptake on sampling lines which can be a significant problem with ammonia and amines

Johnson Space Center's regenerative life support systems test bed

The Regenerative Life Support System (RLSS) Test Bed at NASA's Johnson Space Center is an atmospherically closed, controlled environment facility for the evaluation of regenerative life support systems using higher plants in conjunction with physicochemical life support systems. When completed, the facility will be comprised of two large scale plant growth chambers, each with approximately 10 m(exp 2) growing area. One of the two chambers, the Variable Pressure Growth Chamber (VPGC), will be capable of operating at lower atmospheric pressures to evaluate a range of environments that may be used in Lunar or Martian habitats; the other chamber, the Ambient Pressure Growth Chamber (APGC) will operate at ambient atmospheric pressure. The root zone in each chamber will be configurable for hydroponic or solid state media systems. Research will focus on: (1) in situ resource utilization for CELSS systems, in which simulated lunar soils will be used in selected crop growth studies; (2) integration of biological and physicochemical air and water revitalization systems; (3) effect of atmospheric pressure on system performance; and (4) monitoring and control strategies

ESTIMATES OF DEMAND RELATIONSHIPS FOR APRICOTS AND APRICOT PRODUCTS

Apricots are a unique commodity in that they are used in four ways: for fresh markets and for canning, freezing, and drying. This article formulates a model of the demand system for this commodity and presents FIML and 2SLS estimates of the simultaneous components of the system. The empirical findings include estimates of price flexibilities and elasticities and equations that predict prices and allocations among product forms, given the annual production.Demand and Price Analysis,

Acyloxylation of Cyclic Enones: Synthesis of Densely Oxygenated Guaianolides

The α′-acyloxylation of cyclic enones with linear carboxylic acids is described. The reaction is promoted by KMnO4 in the presence of a carboxylic acid and its corresponding carboxylic anhydride. The optimization of the reaction has been carried out using the statistical methodology known as design of experiments. The optimized reaction conditions have been evaluated in terms of substrate scope and compatibility with different functional groups. The methodology has been applied to the synthesis of densely oxygenated guaianes and guaianolides

Safety Assessment of Recycled Polyolefins for Food Contact Applications: Non-Target Screening of Volatile and Non-Volatile Substances

The thesis aims to establish sensitive and reliable sample pre-treatment methods as well as data analysis workflows to identify and quantify migrants from recycled polyolefins. Both volatile and non-volatile substances will be analysed in a non-target screening manne<br /

Synthesis of Trichodermin Derivatives and Their Antimicrobial and Cytotoxic Activities

Trichothecene mycotoxins are recognized as highly bioactive compounds that can be used in the design of new useful bioactive molecules. In Trichoderma brevicompactum, the first specific step in trichothecene biosynthesis is carried out by a terpene cyclase, trichodiene synthase, that catalyzes the conversion of farnesyl diphosphate to trichodiene and is encoded by the tri5 gene. Overexpression of tri5 resulted in increased levels of trichodermin, a trichothecene-type toxin, which is a valuable tool in preparing new molecules with a trichothecene skeleton. In this work, we developed the hemisynthesis of trichodermin and trichodermol derivatives in order to evaluate their antimicrobial and cytotoxic activities and to study the chemo-modulation of their bioactivity. Some derivatives with a short chain at the C-4 position displayed selective antimicrobial activity against Candida albicans and they showed MIC values similar to those displayed by trichodermin. It is important to highlight the cytotoxic selectivity observed for compounds 9, 13, and 15, which presented average IC50 values of 2 g/mL and were cytotoxic against tumorigenic cell line MCF-7 (breast carcinoma) and not against Fa2N4 (non-tumoral immortalized human hepatocytes)

Identification of volatile compounds from polyolefin used for food packaging

Identification of volatile compounds from different virgin polyolefin FCMs was carried out by GC-MS with both HS-SPME and ultrasonic extraction (UE), with the aim to obtein the most amount of volatile compounds from polyolefin. Seventy compounds were identified with 90% reliability by GC-MS with NIST 14 library, most of them are NIAS. &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp; &nbsp

Atmospheric Solids Analysis Probe (ASAP) and Atmospheric Pressure Gas Chromatography (APGC) coupled to Quadrupole Time of Flight Mass Spectrometry (QTOF-MS) as alternative techniques to trace aromatic markers of mineral oils in food packaging

The aim of this work was to select and identify the best markers of aromatic hydrocarbon mineral oil (MOAH) in food packaging. For this purpose, a series of mineral oils was initially analysed. Polycyclic Aromatic Hydrocarbons (PAHs) and the alkylated isomers of Methylnaphthalene (MNS), Diisopropylnaphtalene (DIPNs), Dibenzothiophenes (DBTS), Methyldibenzothiophene (MDBTs), Dimethyldibenzothiophenes (DMDBTs) and Benzonaphthiophenes (BNTS) were then explored. Their presence was confirmed by direct analysis of several mineral oils by Atmospheric Solids Analysis Probe Quadrupole-Time of Flight Mass Spectrometry (ASAP-QTOF-MS). Atmospheric Pressure Gas Chromatography Quadrupole-Time of Flight Mass Spectrometry (APGC-QTOF-MS) was used to confirm the markers in different samples of oils, recycled PET (rPET), recycled cardboard and packaging of couscous and semolina to confirm the contamination. 27 markers were found in the mineral oil samples, 22 of them in rPET, 8 in recycled board and no MOAH were found in packaging of couscous and semolina