Evaluation of PLE exhaustiveness for the extraction of PCBs from sediments and the influence of sediment characteristics

Pressurized liquid extractions were performed on eight sediments in order to investigate if a modified US EPA method (100 °C, 100 bar, n-heptane/acetone (1:1), 2 × 5 min) provided exhaustive extractions of polychlorinated biphenyls (PCBs) from sediment, and to study if the extractability of PCBs from the different sediments was affected by characteristics of the sediment. The recovery from the eight native sediments, contaminated in nature, was between 96.4% and 98.9%, as an average of the recoveries from 10 PCB congeners. Hundred percent recovery was defined as the sum of two consecutive extractions (2 × 5 min each) at the stated conditions. The recoveries of the individual congeners were above 94%, except for one congener in one sediment, which had a recovery of 92%. When the recoveries and different characteristics of the sediments were compared, no correlation appeared between recoveries and sediment PCB concentration, total organic carbon (TOC), soot carbon (SC) or amorphous carbon (AC). The fact that carbon did not influence the extractions was somewhat surprising, since previous experiments have indicated a connection. Instead, statistically significant (p < 0.05) correlations were observed for water content and carbon/nitrogen (C/N) ratio. The decrease in recoveries with decreased water content was attributed to less access of the solvent to the analytes due to less matrix swelling. The lowered recoveries with increased C/N ratio can indicate that a difference in structure of the organic matter exists, which influences the binding strength between the analytes and the matrix. The difference in structure can possibly be explained by different origin of the organic matter or by aging effects. Overall the method was found to be exhaustive and the excellent recoveries show that sediment characteristics do not influence the extractions markedly.     

Selective pressurized liquid extraction of polychlorinated biphenyls from fat-containing food and feed samples influence of cell dimensions, solvent type, temperature and flush volume

Sulphuric acid impregnated silica was used for the lipid free extraction of polychlorinated biphenyls from fat containing food and feed matrices using pressurized liquid extraction on a Dionex ASE300, with 34 mL cells. Data were compared to a previous publication where extractions had been performed on a Dionex ASE200, with 33 mL cells. Four different fat/fat retainer ratios (FFRs) were tested (0.100, 0.075, 0.050 and 0.025) at 50 and 100 degrees C using n-pentane, n-hexane or n-heptane as extraction solvent. The best results were obtained with a FFR of 0.025 when applying a temperature of 100 degrees C. Both n-pentane and n-heptane were capable of replacing n-hexane as extraction solvent. A flush volume of 60% was sufficient as suggested in US Environmental Protection Agency Method 3545. The applicability of the method was demonstrated for naturally contaminated fish meal as well as various spiked and certified materials.     

Microwave-assisted extraction of zearalenone from wheat and corn

A microwave-assisted extraction (MAE) method has been developed for determination of zearalenone in wheat and corn by LC-MS with an atmospheric pressure chemical ionization interface (APCI). Matrix effects were minimized by use of matrix-matched standard curves for quantification of the analyte. The limit of quantification (LOQ) of the method was 30 ng g(-1) in wheat and 20 ng g(-1) in corn. The rapid LC-MS method enabled analysis of the extracts without clean-up, thereby reducing analyte losses, the time required for the analytical procedure, and costs. A factorial design approach was used to examine the effect on extraction efficiency of the main extraction conditions - time, temperature, and solvent. On the basis of results from statistical assessment extraction was performed with 1:1 (v/v) methanol-acetonitrile at 80 degrees C for 5 min. When these extraction conditions were applied to a wheat sample from a recently conducted international proficiency test, 92% (103 ng g(-1)) of the assigned zearalenone concentration (112 ng g(-1)) in the test material was obtained. This result was within the uncertainty (u) range of the assigned value of the test material (u=+/-15.8 ng g(-1), alpha=0.05) thereby demonstrating the accuracy of the method was sufficient. The precision of the whole method was also confirmed to be adequate, because the observed relative standard deviation (RSD) of 12% (n=10) also fulfils the quality criteria recommended by European guidelines for in-house method validation.     

Reaction of pyridine N-oxides with Grignard reagents: a stereodefined synthesis of substituted dienal oximes

Rapid addition of Grignard reagents to pyridine N-oxides under mild conditions gave stereodefined dienal oximes in good to excellent yields. This reaction provides an efficient access to substituted olefins with defined stereochemistry that are potentially of interest as bioactives themselves or as versatile synthetic intermediates.     

Selective determination of organophosphate flame retardants and plasticizers in indoor air by gas chromatography, positive-ion chemical ionization and collision-induced dissociation mass spectrometry

Gas chromatography/ion trap mass spectrometry with in-source ionization and dissociation was used in positive-ion chemical ionization (PICI) mode for the determination of organophosphate triesters in indoor air. These compounds are widely used as additive flame retardants and plasticizers in different types of materials and have become ubiquitous pollutants in indoor environments. When using collision-induced dissociation in PICI mode the fragmentation of the organophosphate triesters can be performed in a more controllable way than in electron ionization (EI) mode. The developed selected-reaction monitoring method provided high selectivity for the investigated compounds. For 8-h air measurements (corresponding to 1.5 m3 of sampled air) the limit of detection of the method was determined to be in the range 0.1-1.4 ng m(-3), which is comparable with nitrogen-phosphorus detection and about 50-fold lower than when using EI in selected-ion monitoring mode. The presented method was applied to samples from three common indoor environments, in which a number of organophosphate triesters were identified and quantified. The dominating compound was found to be tris(2-chloropropyl) phosphate, which occurred at levels up to 0.8 microg m(-3).     

Determining PCB desorption behaviour on sediments with SFE and investigating the dependency of selective fractions on sediment characteristics

A method for studying PCB desorption behaviour from sediments using supercritical fluid extraction (SFE) and pressurized liquid extraction (PLE) is presented. Four sediments were investigated and extracted with supercritical carbon dioxide employing increasingly harsher extraction conditions ranging from 40°C and 12?MPa to 100°C and 36.5?MPa. To ensure quantitative extractions, the remaining SFE residues were also extracted with PLE. Resulting profiles identified at least three different PCB fractions within the four sediments. Furthermore, a distinct fraction was obtained with extraction for 2?h at 40°C and 36.5?MPa. This fraction has previously been found to correlate well with bioavailable fractions. The dependency of this fraction on sediment total organic carbon (TOC) was investigated, both for sediments examined in this study as well as for previously reported values using the same extraction conditions. It was found that TOC does not correlate to selective SFE, which indicates that the use of TOC to predict bioavailability is questionable.     

Selective pressurized liquid extraction of polychlorinated biphenyls in sediment.

A selective pressurized liquid extraction procedure (SPLE) was developed for a fast determination of polychlorinated biphenyls in sediment. The final method was performed at 100 degrees C with heptane/dichloromethane (90:10, v/v) as extraction solvent for 2x5 min. Sulfuric acid impregnated silica was placed downstream of the sample in the extraction cell to remove interfering components. This simultaneous extraction/clean-up was performed in 20 min, with an average congener recovery of 92% compared to a classical 24 h Soxhlet methodology and 2 h of external manual clean-up.     

Determination of steroid hormones in blood by GC–MS/MS

This paper presents the development, optimization and validation of a methodology to determine nine key steroid hormones (viz. pregnenolone, progesterone, dehydroepiandrosterone, androstenedione, testosterone, dihydrotestosterone, estrone, 17α-estradiol and 17β-estradiol) expressed in the steroidogenesis in biological fluids. The analytical method allows for the determination of steroid hormones in blood plasma and serum down to 0.08–0.16 ng/mL for estrogens, 0.20–0.36 ng/mL for androgens and 0.36–0.43 ng/mL for progestagens. These limits of detection were obtainable using a two-step solid-phase clean-up for fractionation and elimination of interfering lipids (fatty acids, phospholipids, glycerides and sterols) from the steroid hormones. The accuracy of the method was 50–112% in the range 0.10 to 2.00 ng/mL.     

Microspectrofluorometric identification of noradrenaline and 5-hydroxytryptamine on silica gel thin-layers

Summary Catecholamines and indolamines react with formaldehyde to form fluorescent condensation products. This reaction forms the basis for the histochemical method of Falck and Hillarp which permits the demonstration of monoamines at the cellular level. The formation of the fluorophores is believed to require the presence of catalyzing proteins, peptides or amino acids. A similar reaction, however, can be induced also on silica gel thin-layers and this has been utilized for micro-analysis of tissue amines. In the present study formaldehyde-induced fluorophores of noradrenaline and 5-hydroxytryptamine in dry protein films and on silica gel thin-layers were analysed by microspectrofluorometry. The results indicated that the fluorophores formed in protein films and in silica gel were identical. It is suggested that the reaction on thin-layers can be used as a convenient model system permitting a detailed analysis of the various steps in the histochemical technique for the demonstration of catecholamines and 5-hydroxytryptamine.

---

Zusammenfassung Catecholamine und Indolamine reagieren mit Formaldehyd zu fluorescierenden Kondensationsprodukten, die bei der histochemischen Methode von Falck u. Hillarp die Sichtbarmachung von Monoaminen im Gewebe ermöglichen. Die Bildung von fluorescierenden Produkten erfordert anscheinend die Gegenwart von katalysierenden Proteinen, Peptiden oder Aminosäuren. Eine ähnliche Reaktion kann jedoch auch auf Kieselgel-Dünnschichten erhalten werden. Dieses Modell wurde für die Mikroanalyse von Ammen im Gewebe angewandt. In der vorliegenden Untersuchung wurden fluorescierende Kondensationsprodukte aus Noradrenalin und 5-Hydroxytryptamin und p-Formaldehyd in getrockneten Proteinfilmen und auf Kieselgel-Dünnschichten mit Hilfe der Mikrospektrofluorometrie analysiert, wobei sich ergab, daß diese Produkte in beiden Fällen vollkommen übereinstimmten. Es wird vorgeschlagen, die Reaktion auf Dünnschichten als geeignetes Modellsystem anzuwenden, das eine genaue Analyse der verschiedenen Schritte in der histochemischen Technik zur Sichtbarmachung von Catecholaminen und 5-Hydroxytryptamin ermöglicht.

     

Ergodic theorems for coset spaces

We study in this paper the validity of the Mean Ergodic Theorem along left Følner sequences in a countable amenable group G. Although the Weak Ergodic Theorem always holds along any left Følner sequence in G, we provide examples where the Mean Ergodic Theorem fails in quite dramatic ways. On the other hand, if G does not admit any ICC quotients, e.g., if G is virtually nilpotent, then the Mean Ergodic Theorem holds along any left Følner sequence. In the case when a unitary representation of a countable amenable group is induced from a unitary representation of a “sufficiently thin” subgroup, we show that the Mean Ergodic Theorem holds for the induced representation along any left Følner sequence. Furthermore, we show that every countable (infinite) amenable group L embeds into a countable (not necessarily amenable) group G which admits a unitary representation with the property that for any left Følner sequence (F_n) in L, there exists a sequence (s_n) in G such that the Mean (but not the Weak) Ergodic Theorem fails in a rather strong sense along the (right-translated) sequence (F_ns_n) in G. Finally, we provide examples of countable (not necessarily amenable) groups G with proper, infinite-index subgroups H, so that the Pointwise Ergodic Theorem holds for averages along any strictly increasing and nested sequence of finite subsets of the coset G/H.