Electrospray ionization mass spectrometric studies on the amphoteric surfactant cocamidopropylbetaine.

After liquid chromatographic (LC) separation, electrospray ionization mass spectrometry (ESI-MS) was investigated for the determination of the amphoteric surfactant cocamidopropylbetaine (CAPB). In the positive ion mode the molecule formed the adduct ions [M + H](+), [M + Na](+) and [M + K](+). Adducts of these cations were also detected with decreasing abundance as dimer and trimer clusters. Additionally, doubly charged molecular ions with different combinations of cations were identified. It was noticed that the relative abundances of individual cation adducts were not reproducible, apparently owing to varying contents of alkali metal ions originating from the solvent and the sample. Under negative ionization, the major molecular ion was [M - H](-). Higher clusters formed by two and three surfactant molecules, i.e. [2M - H](-) and [3M - H](-) were likewise registered. The tendency to form clusters in both positive and negative ion modes, even at 0.1 mg l(-1) levels, was attributed to strong electrostatic interactions between the zwitterionic head groups. Further evidence for this assumption was provided by the detection of a fragment formed from [2M - H](-) which contained the two charged head groups. Studies were undertaken in the negative ion mode on the concentration- and orifice voltage-dependent monomer, dimer and trimer formation of C(12)-CAPB in order to evaluate potential issues in using the ion [M - H](-) mode for quantitative analysis. Finally, the established (-)-LC/ESI-MS method was applied to follow up the primary degradation of CAPB in a laboratory-scale fixed-bed bioreactor (FBBR) spiked with a test concentration of 10 mg l(-1). Direct analysis without sample pretreatment revealed that higher alkyl homologues were more prone to adsorption. Primary biodegradation of all alkyl homologues was completed after a period of 4 days. Selected lyophilized FBBR samples were examined for the presence of transient or stable degradation intermediates, but no metabolite could be identified.     

The Adsorption of Polyvinylpyrrolidone on Kaolinite Saturated with Sodium Chloride

The adsorption of two different molecular weights of polyvinylpyrrolidone (PVP) (M(w)=44,000 and M(w)=360,000 g mol(-1)) from water on kaolinite saturated with sodium chloride has been studied. The adsorption of PVP increases slowly as temperature increases. The adsorption of PVP on the kaolinite was studied by considering Fourier transform infrared (FTIR) spectra, X-ray diffraction patterns, and dielectric constants. During the adsorption process, PVP interacts with saturating sodium cations and possibly forces some of them onto the edges of the kaolinite; thus, the dielectric constant of saturated kaolinite is reduced after PVP adsorption. Copyright 2001 Academic Press.     

omega-(Bis(trifluoromethyl)amino)alkane-1-sulfonates: synthesis and mass spectrometric study of the biotransformation products

In search of fluorinated functional groups which could undergo defluorination, and therefore be included in novel non-polluting fluorinated surfactants, omega-(bis(trifluoromethyl)amino)alkane-1-sulfonates (BTFMA-AS) with a homologue distribution from seven to thirteen methylene groups were synthesized and investigated for aerobic biodegradation applying both a standardized test and a fixed-bed bioreactor (FBBR). These compounds were prepared as part of a screening study for potentially mineralizable fluorinated endgroups.Application of hybrid triple quadrupole-linear ion trap mass spectrometry (QqQ(LIT)-MS) coupled to high-performance liquid chromatography (HPLC) allowed the tracking of primary degradation as well as the detection and structural elucidation of biotransformation intermediates. An understanding of the fragmentation pathway of the test compounds allowed selective precursor ion scans to reveal the presence of stable fluorinated metabolites. Structures were confirmed by enhanced product ion scans and MS(3) scans in the linear ion trap mode.The primary biodegradation rate and the extent of biodegradation were found to be chain-length dependent, with higher homologues being completely primarily degraded within 10 days. For the first time, two simultaneous metabolic pathways for substituted linear alkane-1-sulfonates were discovered: Desulfonation, oxidation to a carboxylic acid and subsequent chain-length shortening by beta-oxidation dominated the metabolism. This pathway resulted in the formation of 3-(bis(trifluoromethyl)amino)propionic acid and bis(trifluoromethyl)aminoacetic acid, which showed recalcitrance in this experiment. Oxidation of the alkyl chain to the respective carbonyl derivative represents the minor pathway. Only the long-chain homologues of these oxidized species were partially degraded; the short-chain homologues were not attacked.     

Anaerobic biodegradation tests of poly(lactic acid) and polycaprolactone using new evaluation system for methane fermentation in anaerobic sludge

The anaerobic biodegradation tests of polycaprolactone (PCL) and poly(lactic acid) (PLA) powders were done at thermophilic temperature (55 °C) under aquatic conditions (total solid concentrations of the used sludge were 1.73% (undiluted sludge) and 0.86% (diluted sludge)) using a newly developed evaluation system. With this system, the evolved biogas is collected in a gas sampling bag at atmospheric pressure. This method is more convenient than using a pressure transducer or inverted graduated cylinder submerged in water. The biodegradation of PCL powder (10 g, 125–250 μm) in the diluted sludge stopped in about 47 days when the biodegradability reached 92%. The biodegradability of PLA powder (10 g, 125–250 μm) in undiluted sludge was 91% at about 75 days. The biodegradability of PLA powder (10 g, 125–250 μm) in diluted sludge was 79% at about 100 days. The biodegradability of PLA powder (5 g, 125–250 μm) in diluted sludge was 80% at about 85 days. It was found that the PCL and PLA powders were quite degraded using the new evaluation method. In addition, the smaller particle size PCL powder was biodegraded faster.     

表面活性剂和聚乙烯吡咯烷酮在ZrO2上的吸附对其悬浮体稳定性的影响

研究了水溶液中十二烷基苯磺酸钠（ＳＤＢＳ）、溴代十四烷基吡啶（ＴＰＢ）和聚乙烯吡咯烷酮（ＰＶＰ）在ＺｒＯ２上的吸附及对ＺｒＯ２水悬浮体稳定性的影响。结果表明：ｐＨ＝２．４时ＳＤＢＳ在ＺｒＯ２上的吸附等湿线为ＬＳ型，ｐＨ＝７．０时ＴＰＢ的吸附等温线为Ｓ型，吸附等温线与ＺｒＯ２粒子ζ电势变化同线有大体一致的关系。在最大吸附量时ＺｒＯ２粒子ζ电势较大，且吸附的表面活性剂离子形成大部分亲水基朝向水相的表面     

Bioplastic biodegradation activity of anaerobic sludge prepared by preincubation at 55 °C for new anaerobic biodegradation test

The new method to evaluate the anaerobic biodegradability of bioplastics, such as polycaprolactone (PCL) and poly (lactic acid) (PLA), under aquatic (slurry) conditions at 55 °C is applying. For this method, we prepared the sludge at 55 °C from the sludge at 37 °C by the method in which the sludge from the real tank operating at around 37 °C using cow manure and vegetable waste as the feed stock was preincubated at 55 °C. It was unknown at which stage the sludge during preincubation has the optimized anaerobic biodegradation activity of plastics. Four different stage sludges during preincubation (the sludge at 7 days after the start of preincubation at 55 °C, at 12 days, at 18 days, and at 40 days) were compared by the anaerobic biodegradation activity of PLA. The preincubated sludge at around 18 days (a gradual decrease in biogas evolution and a methane ratio over 60%) showed the highest biodegradation activity of PLA. In addition, the bacterial population in each sludge was analyzed by the denaturing gradient gel electrophoresis (DGGE) analysis of the amplified 16S rRNA gene fragments, however, the newly grown bacteria bands at 55 °C were not clearly detected.     

Association between branched poly(ethyleneimine) and sodium dodecyl sulfate in the presence of neutral polymers

In the present paper, the effect of different neutral polymers on the self-assemblies of hyperbranched poly(ethyleneimine) (PEI) and sodium dodecyl sulfate (SDS) has been investigated at different ionization degrees of the polyelectrolyte molecules. The investigated uncharged polymers were poly(ethyleneoxide), poly(vinylpyrrolidone) and dextran samples of different molecular mass. Dynamic light scattering and electrophoretic mobility measurements demonstrate that the high molecular mass PEO or PVP molecules adsorb considerably onto the surface of the PEI/SDS nanoparticles. At appropriate concentrations of PVP or PEO, sterically stabilized colloidal dispersions of the polyelectrolyte/surfactant nanoparticles with hydrophobic core and hydrophilic corona can be prepared. These dispersions have considerable kinetic stability at high ionic strengths where the accelerated coagulation of the PEI/SDS nanoparticles results in precipitation in the absence of the neutral polymers. In contrast, the addition of dextran does not affect considerably the kinetic stability of PEI/SDS mixtures because of its low adsorption affinity towards the surface of the polyelectrolyte/surfactant nanoparticles.     

Biodegradation of PVA-based formulations

Investigation of the biodegradability of water soluble poly(vinyl alcohol) (PVA) based blown films was carried out under different lab-scale environmental conditions. In particular respirometric tests were utilized in order to evaluate the biodegradability of PVA films in composting, in modified Sturm test and in soil burial simulation tests. Several microbial inocula present in river water, mature compost, forest and farm soils as well as sewage sludge from municipal and paper mill wastewater treatments plants were utilized for the relevant tests. A mixed PVA-degrading microbial culture was obtained by a common enrichment procedure by using sewage sludge from paper mill as inoculum; this culture was tentatively utilized for the isolation of single PVA-degrading microorganisms. As a first result we can stress that significant biodegradation extent in fairly low incubation time can be obtained only in the presence of acclimated microbial populations such as those deriving from paper mill sewage sludge, in liquid cultures. Nevertheless separation of single degrading microbial species was impossible most likely due to the establishment of symbiotic or commensal interactions between the single components of the PVA-degrading mixed cultures. On the other hand, limited mineralization rates were recorded in solid cultures in the presence of soil or compost. Finally, a mechanism of degradation of polymer chains unlike random or unzipping was suggested in the presence of either PVA-degrading mixed culture and its filtrate by means of viscometric determinations of molecular weight within the time.     

Mechanistic studies in biodegradation of the new synthesized fluorosurfactant 9-[4-(trifluoromethyl)phenoxy]nonane-1-sulfonate

As a new potentially mineralizable fluorinated surfactant, 9-[4-(trifluoromethyl)phenoxy]nonane-1-sulfonate was synthesized and exposed to a standardized Zahn-Wellens test (OECD 302B). After the release of fluoride indicating the mineralization of the trifluoromethyl group, 9-[4-(trifluoromethyl)phenoxy]nonane-1-sulfonate was subjected to a further biodegradation test carried out in a fixed bed bioreactor (FBBR). Evolution of biodegradation routes and pursuit was done by quadrupole linear ion trap mass spectrometer (QqLIT-MS) and quadrupole time-of-flight tandem mass spectrometer (QqTOF-MS). Biotransformation was initiated via hydroxylation in the alkyl chain at different positions. Hydroxy-9-[4-(trifluoromethyl)phenoxy]nonane-1-sulfonate was further oxidized with subsequent scission of the molecule forming mainly p-(trifluoromethyl)phenolate, which was mineralized releasing inorganic fluoride. These results demonstrate, that the new synthesized fluorosurfactant 9-[4-(trifluoromethyl)phenoxy]nonane-1-sulfonate is completely biotransformed. However, some intermediates, depending on the position of hydroxylation, impede further mineralization.     

Impedance analysis of an electrode-separated piezoelectric sensor as a surface-monitoring technique for gelatin adsorption on quartz surface

The early events pertaining to gelatin adsorption and desorption onto quartz surfaces were studied, employing an electrode-separated piezoelectric sensor (ESPS). The adsorption of gelatin on a quartz crystal surface corresponds to a mass increase, which can be monitored in real time by the changes in the impedance parameters of the ESPS. It was shown that the adsorption of gelatin on a quartz surface is partly irreversible with respect to the dilution of the bulk phase. The observed adsorption kinetics is compatible with a mechanism that involves adsorption, desorption, and transformation from a reversible adsorption state to irreversible one. A progressive approach method was established to simulate the adsorption process. The adsorption densities and kinetic parameters in the early adsorption process were obtained from the responses of the ESPS in the adsorption process. The influence of pH and ionic strength was tested. A comparison with the Langmuir adsorption model was made.     

Impact of Various Parameters Over the Adsorption of Polyvinylpyrrolidone onto Kaolin

The adsorption of water-soluble polymer, polyvinylpyrrolidone having molecular mass 9.1 ± 1.43 × 10³Kg mole^?1 on kaolin has been investigated. The effect of different parameters like pH, molecular mass of polymer and pre-heat treatment on the adsorption of PVP has been deliberated. The 20.7% decrease in adsorption in pH ranging from 2–10 have been found, which was an indication of the fact that with the increase in pH the kaolin surfaces sites charge amount and ultimately sign changes. Maximum adsorption was observed at pH 5.6 that was also molecular mass dependent. By increasing the pretreatment temperature, the amount of polymer adsorbed was also increased. However, above the specific temperature adsorption of PVP was decreased and attributed to decrease in specific surface area of kaolin.     

Nanoparticle formation of poorly water-soluble drugs from ternary ground mixtures with PVP and SDS

Poorly water-soluble drugs N-5159, griseofulvin (GFV), glibenclamide (GBM) and nifedipine (NFP) were ground in a dry process with polyvinylpyrrolidone (PVP) and sodium dodecyl sulfate (SDS). Different crystallinity behavior of each drug during grinding was shown in the ternary Drug/PVP/SDS system. However, when each ternary Drug/PVP/SDS ground mixture was added to distilled water, crystalline nanoparticles which were 200 nm or less in size were formed and had excellent stability. Zeta potential measurement suggested that the nanoparticles had a structure where SDS was adsorbed onto the particles that were formed by the adsorption of PVP on the surface of drug crystals. Stable existence of crystalline nanoparticles was attributable to the inhibition of aggregation caused by the adsorption of PVP and SDS on the surface of drug crystals. Furthermore, the electrostatic repulsion due to the negative charge of SDS on a shell of nanoparticles could be assumed to contribute to the stable dispersion.     

External validation of EPIWIN biodegradation models

The BIOWIN biodegradation models were evaluated for their suitability for regulatory purposes. BIOWIN includes the linear and non-linear BIODEG and MITI models for estimating the probability of rapid aerobic biodegradation and an expert survey model for primary and ultimate biodegradation estimation. Experimental biodegradation data for 110 newly notified substances were compared with the estimations of the different models. The models were applied separately and in combinations to determine which model(s) showed the best performance. The results of this study were compared with the results of other validation studies and other biodegradation models. The BIOWIN models predict not-readily biodegradable substances with high accuracy in contrast to ready biodegradability. In view of the high environmental concern of persistent chemicals and in view of the large number of not-readily biodegradable chemicals compared to the readily ones, a model is preferred that gives a minimum of false positives without a corresponding high percentage false negatives. A combination of the BIOWIN models (BIOWIN2 or BIOWIN6) showed the highest predictive value for not-readily biodegradability. However, the highest score for overall predictivity with lowest percentage false predictions was achieved by applying BIOWIN3 (pass level 2.75) and BIOWIN6.     

Biodegradabilities of some chain oils in groundwater as determined by the respirometric BOD OxiTop method

The respirometric BOD OxiTop method was used to monitor the biodegradation of different chain oils (mineral, rapeseed and tall oils) over 28 days in groundwater, as well as in standard conditions described by OECD 301 F. The aim of the study was to gather more information about the biodegradability of forestry oils in groundwater, as well as about the suitability of the automatic OxiTop method for biodegradation measurements. The BOD OxiTop method proved to be a precise and reliable technique for determining the biodegradations of different oils. Some comparative studies were also made using a traditional IR method in order to clarify the total oil concentrations. The results show that if biodegradation only is to be monitored, the OxiTop method is preferable. This is due to the influence of other reactions aside from biodegradation on total hydrocarbon concentrations when using the IR method.     

Read-across of ready biodegradability based on the substrate specificity of N-alkyl polypropylene polyamine-degrading microorganisms

The biodegradation of N-alkyl polypropylene polyamines (NAPPs) was studied using pure and mixed cultures to enable read-across of ready biodegradability test results. Two Pseudomonas spp. were isolated from activated sludge with N-oleyl alkyl propylene diamine and N-coco alkyl dipropylene triamine, respectively. Both strains utilized all NAPPs tested as the sole source of carbon, nitrogen and energy for growth. Mineralization of NAPPs was independent of the alkyl chain length and the size of the polyamine moiety. NAPPs degraded in closed bottle tests (CBTs) using both river water and activated sludge. However, ready biodegradability of NAPPs with alkyl chain lengths of 16–18 carbon atoms and polyamine moieties with three and four nitrogen atoms could not be demonstrated. Biodegradation in the CBT was hampered by their limited bioavailability, making assessment of the true ready biodegradability of these highly adsorptive surfactants impossible. All NAPPs are therefore classified as readily biodegradable through read-across. Read-across is justified by the broad substrate specificity of NAPP-degrading microorganisms, their omnipresence and the mineralization of NAPPs.     

Standardization of activated sludge for biodegradation tests

Activated sludges are an inoculum source commonly used in biodegradation studies, as wastewater treatment facilities constitute an entry point to the environment for many chemicals. In this paper, the main issues relating to the use of activated sludge in biodegradability tests are presented. Special attention is also devoted to discussing the factors affecting both the activity of the microbial communities and the test results. After a short survey of the state of the art of microbiology of activated sludge, the paper focuses on the methods used to reduce the variations in the diversity, quality and quantity of these communities. Finally, use of surrogates as reference materials in biodegradability tests is discussed.     

Immobilization of peroxidase on SiO2 surfaces with the help of a dendronized polymer and the avidin-biotin system

Horseradish peroxidase (HRP) is immobilized in three easy steps on SiO(2) surfaces with the help of a polycationic second generation dendronized polymer (denpol) and the biotin-avidin system. This stepwise immobilization process is monitored and quantitatively analyzed with the transmission interferometric adsorption sensor. Partially biotinylated denpol is first adsorbed onto SiO(2) , followed by addition of avidin and then of biotinylated HRP. Denpols in their molecular structure combine properties of polymers as well as dendrimers which are found to be of clear advantage for this type of non-covalent enzyme immobilization. With respect to the reproducibility of the adsorption process and with respect to the stability of the adsorbed polymer layer, the denpol is superior to α-poly-D-lysine which is used as a reference polymer. Furthermore, HRP immobilized with the denpol on commercial glass slides remains considerably more active upon storage as compared to HRP immobilized with the help of α-poly-D-lysine with a similar number of repeating units. The ease of the denpol-mediated HRP immobilization and the high stability of the immobilized enzyme are promising for bioanalytical applications.     

A kinetic model for predicting biodegradation

Biodegradation plays a key role in the environmental risk assessment of organic chemicals. The need to assess biodegradability of a chemical for regulatory purposes supports the development of a model for predicting the extent of biodegradation at different time frames, in particular the extent of ultimate biodegradation within a '10 day window' criterion as well as estimating biodegradation half-lives. Conceptually this implies expressing the rate of catabolic transformations as a function of time. An attempt to correlate the kinetics of biodegradation with molecular structure of chemicals is presented. A simplified biodegradation kinetic model was formulated by combining the probabilistic approach of the original formulation of the CATABOL model with the assumption of first order kinetics of catabolic transformations. Nonlinear regression analysis was used to fit the model parameters to OECD 301F biodegradation kinetic data for a set of 208 chemicals. The new model allows the prediction of biodegradation multi-pathways, primary and ultimate half-lives and simulation of related kinetic biodegradation parameters such as biological oxygen demand (BOD), carbon dioxide production, and the nature and amount of metabolites as a function of time. The model may also be used for evaluating the OECD ready biodegradability potential of a chemical within the '10-day window' criterion.