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.     

Oil-Water Partitioning of a Synthetic Tetracarboxylic Acid as a Function of pH

The oil-water partitioning of a synthetic tetraacid acting as a model compound for indigenous C₈₀-C₈₂ ARN acids has been studied as a function of pH, ionic strength and type of monovalent counterion. Experimental data obtained with ultraviolet-visible and HPLC/UV analyses have been fitted to thermodynamic models based on one, two or four dissociation steps to obtain o/w partition coefficients (K _wo ) of the fully protonated acid between chloroform and aqueous solutions, and its apparent acidity constant(s), pK _a. As the study is conducted above the CMC of the tetraacid, in general high apparent acidity constants were obtained in the range from 6 to 8 resulting from micellization equilibria. K _wo values were obtained in the range from 10^?3 to 10^?4, and decreasing with increasing salinity. At 50 mM K⁺, no conclusions could be made regarding the number of distinguishable dissociation steps, while at higher ionic strength (184 mM and 452 mM K⁺) and at 184 mM Na⁺ a model with two dissociation steps provided good fits to the experimental data. The first step was found to be given by a pK _a ≈ 6.6–6.8 and the second dissociation step at pK _a values ≈ 7.8–8.3. The two-step mechanism supports previous results obtained by potentiometric titrations. No significant difference in the o/w behavior was observed when changing the counterion from potassium to sodium. The main partitioning of the tetraacid in the aqueous phase occurred above pH 8, where the fully deprotonated acid was formed.     

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.     

Langmuir films of asphaltene model compounds and their fluorescent properties

The relationship between the physicochemical properties of asphaltenes and asphaltene structure is an issue of increasing focus. Surface pressure-area isotherms of asphaltene model compounds have been investigated to gain more knowledge of their arrangement at an aqueous surface. Variations in interfacial activity have been correlated to proposed arrangements. The presence of a carboxylic acid has shown to be crucial for their interfacial activity and film properties. The acid group directs the molecules normal to the surface, forming a stable monolayer film. The high stability was absent when no acidic groups were present. Fluorescence spectra of deposited Langmuir-Blodgett films showed only the presence of the excimer emission for thin films of acidic model compounds, indicating a close face-to-face arrangement of the molecules. Time-correlated single photon counting (TCSPC) of the model compounds in toluene indicated the presence of aggregates for two of four compounds at low concentrations. However, a sudden drop of interfacial tension observed could not be correlated to the aggregation. Instead, aggregation induced by addition of a "poor" solvent showed decreased interfacial activity when aggregated due to decrease of monomers in bulk. The findings regarding these asphaltene model compounds and their structural differences show the great effect an acidic group has on their physicochemical properties.