Irena Budnik

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.

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.

Biodegradation of Oxyethylated Fatty Alcohols by Bacterium Pseudomonas alcaligenes; AE Biodegradation by Pseudomonas alcaligenes

Abstract Pseudomanas alcaligenes is a Gram-negative soil bacteria which has the potential to degrade hydrocarbons including aromatic compounds. The biodegradation of a representative oxyethylated fatty alcohol by the PA strain under static model conditions with a surfactant as a sole source of organic carbon was investigated. Polydispersal oxyethylated dodecanol C12E10 is biodegraded by the bacterial P. alcaligenes strain of following two alternative pathways: central fission with formation of poly(ethylene glycols) or ω-oxidation of an oxyethylene chain with the formation of carboxyl end group and intermediate aldehyde group. Shorter homologues of polydispersal mixture C12E10 are faster biodegraded and the mixture is enriched with longer homologues.