Joanna Zembrzuska

Simultaneous quantitation and identification of organic and inorganic selenium in diet supplements by liquid chromatography with tandem mass spectrometry

A liquid chromatography-tandem mass spectrometry (LC-MS/MS) method was developed for selenium speciation in dietary supplements. Chromatographic separation was performed on a TSK-Gel ODS-100V column using a mixture of 5mM ammonium acetate water solution and methanol as a mobile phase. Conditions chosen for this process allowed to separate all investigated chemical compounds of selenium: seleno-l-methionine, methyl-seleno-l-cysteine, l-selenocystine, methaneseleninic acid, selenite and selenate. A tandem mass spectrometer with an ion trap operating in negative or positive ion mode according to the selenium form being determined was used as a detector. Three extraction procedures: water extraction, enzymatic hydrolysis and sequential extraction were used for preparation of samples for the determination of the actual forms of selenium in diet supplements. The developed method was used for analysis of six dietary supplements containing selenium bought in a pharmacy and supermarket. Apart from speciation analysis of selenium content in supplements total selenium content was determined using instrumental neutron activation analysis (INAA). All expected forms of selenium except for selenite were determined using LC-MS/MS technique. It should be stressed that amounts of selenate were smaller than expected.

Separation and determination of homogenous fatty alcohol ethoxylates by liquid chromatography with mulitstage mass spectrometry

Alcohol ethoxylates (AEs) are a significant component of a stream of surfactants directed to the aquatic environment. The aim of this work was the investigation of the dependence of the analytical signals of homogeneous AE homologues on liquid chromatography with tandem mass spectrometry conditions, as well as the separation of AEs from the water matrix and, on this basis, the development of an analytical procedure suitable for the determination of AEs in environmental samples. Homogeneous homologues containing dodecyl moiety and 2-9 oxyethylene subunits were investigated. The analytical signals of the investigated homologues were optimized in terms of concentration of ammonium acetate in the mobile phase (optimum 5 mM) and a column temperature (optimum 35°C) of the liquid chromatography with tandem mass spectrometry system. A separation of AEs from the water matrix by liquid-liquid extraction (ethyl acetate, chloroform) or solid-phase extraction (C18 , styrene divinylbenzene, H-RX) was investigated. In a model investigation, the best recoveries (>90%) were obtained with a styrene divinylbenzene cartridge eluted with a 1:1 mixture of chloroform and methanol. However, much worse recoveries were obtained from the river water sample. Better results were obtained for liquid-liquid extraction with ethyl acetate. Recoveries of 62-80% were obtained for homologues having 4-9 oxyethylene subunits, at the lowest spike.

Biodegradation of Alcohol Ethoxylates by Bacterial Consortium from Industrial Wastewater

Abstract Industrial waste water, can contain pollutions such as inorganic water-insoluble substances (in particular sewage from electroplating). In nature, the microorganisms play a special role in maintaining life on earth. The decomposition of organic compounds into simple minerals is the main link in the circulation of biogenic elements, especially carbon, nitrogen, phosphorus, sulfur and other. The aim of the study was to evaluate the biodegradability of a model nonionic surfactant and identification of metabolites generated in the process of biodegradation using microbial consortium originating from electroplating wastewater. Tested model nonionic surfactant C12E10 is a mixture of polydisperse homologues of C12Ex, C14Ex and C16Ex series. Alcohol ethoxylates were isolated by liquid-liquid extraction (LLE) using chloroform. Aliquot of the extract was evaporated and reconstituted in the mobile phase for further LC-MS analysis.

Identification of Non-ionic Surfactants in Elements of the Aquatic Environment

Abstract Information concerning the use of non-ionic surfactants (NS) in household products is very scanty. Therefore, a qualitative determination of NS in raw sewage is an alternative source of information concerning the presence and manufacture of NS. The aim of this work was to identify NS in raw sewage (in Poznan and Blonie, both Poland) and treated sewage (in Blonie) and to compare the results with those obtained for river water (Warta in Poznan, Poland). LC-MS/MS was used for this purpose. The presence of 116 ethoxamers, being exclusively polydispersal alcohol ethoxylates (AE) containing alkyl moieties from C10 to C16 and C18, as well as 20 poly(ethylene glycols), was confirmed in the raw sewage, while 68 ethoxamers were found in the treated sewage, including 12 octylphenol ethoxylates. No nonylphenol ethoxylates were identified in the raw or treated sewage.

Removal of Non-Ionic Surfactants in an Activated Sludge Sewage Treatment Plant

Abstract Non-ionic surfactants (NS) are a major source of synthetic organic carbon discharged into surface water. The aim of this work was the investigation of the influence of different factors on NS removal in an activated sludge sewage treatment plant (STP). Tensammetric analytical tools were used for fast and inexpensive NS determination. The STP in Blonie (Poland) was the subject of research. The STPs reconstruction caused a spectacular lowering of NS concentration in the treated sewage; however, in subsequent years, NS concentration significantly rose, due to a dramatic increase in the NS load. The NS load reduction in the reconstructed STP was relatively high (93.4–97.9%). The presence of exclusively alcohol ethoxylates was confirmed in the raw sewage. The residual NS concentration in treated sewage is dependent on the hydraulic retention time, the NS load and on the sludge volume index.

Alkali Metal Cationization of Alkyl Glucosides under Electrospray Ionization Conditions

Abstract Alkyl glucosides have been studied by electrospray ionization mass spectrometry. The effect of the hydrophobic and the hydrophilic parts of these compounds on the stability of [M + Na]+ ions has been evaluated by mass spectra at growing cone voltages. The longer the hydrophobic or the hydrophilic part, the higher the stability of these ions. It has been also found that solvent used affects the abundances of [M + Na]+ ions. In order to check if the radii of alkali metal ions influence the stability of their adducts with the compounds studied, the mass spectra have been recorded for solution containing lithium and potassium ions. The cations of smaller radius form more stable adducts, especially with the compounds having longer hydrophobic parts.

Photodegradation of pyridylketoximes in methanolic solutions under UV–Vis radiation

Photodegradation of the oximes of alkyl-2-, -3-, and -4-pyridylketones and identification of possible degradation products using LC–MS/MS and GC–MS techniques were performed. The influence of copper(II) and iron(III) ions on the stability of the oxime under UV–Vis radiation exposure were also studied. It was found that the photodegradation of the pyridylketoximes resulted in the photoisomerization, photofragmentation and photosubstitution to a pyridine ring. Based on these results, a hypothetical mechanism of photodegradation of pyridylketoximes was proposed.

Removal of hazardous non-steroidal anti-inflammatory drugs from aqueous solutions by biosorbent based on chitin and lignin

The use of chitin modified with kraft lignin as an effective sorbent of ibuprofen and acetaminophen is described for the first time. It was determined how the parameters (contact time, pH, mass of sorbent and temperature) influence the effectiveness of the adsorption process. The adsorption kinetics were calculated using pseudo-first-order, pseudo-second-order (types 1-4) and intra-particle diffusion models, and thermodynamic parameters were determined. The experimental data better correspond to a pseudo-second-order kinetic model of type 1 in the case of both tested pharmaceuticals (r2=0.999). The negative values of ΔH° show the adsorption to be exothermic (-5.515kJ/mol and -5.161kJ/mol for ibuprofen and acetaminophen respectively). Adsorption isotherms, using Langmuir isotherms of types 1-4 and Freundlich model, were also determined. The experimental data better correspond to the Langmuir type 1 model in the case of ibuprofen, and to the Freundlich model in the case of acetaminophen. Desorption tests were carried out to confirm the possibility of reusing the chitin/lignin system. A mechanism of adsorption of ibuprofen and acetaminophen on the chitin/lignin system was also proposed.

Identification of complexes involving thallium(I) and thallium(III) with EDTA and DTPA ligands by electrospray ionization mass spectrometry

Rationale: Thallium is considered as an environmental threat, however its hazardous properties depend on its oxidation state. Tl(III) is approx. 1000-times more toxic compared to Tl(I), therefore identification of each species is essential in order to properly evaluate the associated health hazard. ESI-MS allows determination of speciation in solution due to its soft mode of ionization while selective complexation with ligands allows to distinguish the Tl species. Selective complexation of Tl(I) and Tl(III) ions requires the use of two selective complexing agents and selection of appropriate conditions for this process.

Parallel pathways of ethoxylated alcohol biodegradation under aerobic conditions

Non-ionic surfactants (NS) are a major component of the surfactant flux discharged into surface water, and alcohol ethoxylates (AE) are the major component of this flux. Therefore, biodegradation pathways of AE deserve more thorough investigation. The aim of this work was to investigate the stages of biodegradation of homogeneous oxyethylated dodecanol C12E9 having 9 oxyethylene subunits, under aerobic conditions. Enterobacter strain Z3 bacteria were chosen as biodegrading organisms under conditions with C12E9 as the sole source of organic carbon. Bacterial consortia of river water were used in a parallel test as an inoculum for comparison. The LC-MS technique was used to identify the products of biodegradation. Liquid-liquid extraction with ethyl acetate was selected for the isolation of C12E9 and metabolites from the biodegradation broth. The LC-MS/MS technique operating in the multiple reaction monitoring (MRM) mode was used for quantitative determination of C12E9, C12E8, C12E7 and C12E6. Apart from the substrate, the homologues C12E8, C12E7 and C12E6, being metabolites of C12E9 biodegradation by shortening of the oxyethylene chain, as well as intermediate metabolites having a carboxyl end group in the oxyethylene chain (C12E8COOH, C12E7COOH, C12E6COOH and C12E5COOH), were identified. Poly(ethylene glycols) (E) having 9, 8 and 7 oxyethylene subunits were also identified, indicating parallel central fission of C12E9 and its metabolites. Similar results were obtained with river water as inoculum. It is concluded that AE, under aerobic conditions, are biodegraded via two parallel pathways: by central fission with the formation of PEG, and by Ω-oxidation of the oxyethylene chain with the formation of carboxylated AE and subsequent shortening of the oxyethylene chain by a single unit.