Styrene-acrylonitrile-copolymer and acrylonitrile-butadiene-styrene-copolymer: a study on extractable and migratable oligomers.

Styrene-acrylonitrile-copolymer (SAN) and acrylonitrile-butadiene-styrene-copolymer (ABS) are gaining in importance as food contact materials. Oligomers and other non-intentionally added substances can migrate into foodstuffs. Five SAN and four ABS samples from the German market and manufacturers were extracted and the extractable oligomers were characterised by high performance liquid chromatography-mass spectrometry/ultraviolet detection/chemiluminescence nitrogen detection/fluorescence detection and gas chromatography-mass spectrometry. Trimers, formed from acrylonitrile and styrene units, were determined to be the dominating group of extractable oligomers in SAN and ABS in concentrations of about 4900-15800 mg/kg material. Furthermore, styrene-acrylonitrile dimers, styrene oligomers, styrene monomer and ethylbenzene were identified in the sample extracts. Migration testing with three consecutive migrations for multiple use articles was performed for two SAN articles. Migration of trimers into water, 3% acetic acid, 10% and 20% ethanol under hot-fill conditions (70°C, 2 h) was not detectable above 9 µg/dm2, while 50% ethanol acting as a food simulant for milk (124 µg/dm2 trimers during the third migration) was shown to overestimate the actual migration into milk (< 11 µg/dm2 trimers at 70°C, 2 h). 2-Amino-3-methyl-1-naphthalenecarbonitrile (AMNC), an oligomer degradation product and a primary aromatic amine, was detected in all material sample extracts (0.3-17.1 mg/kg material) and was released into food simulants in low amounts (< 0.014 µg/dm2 during the third migration into 50% ethanol at 70°C, 2 h).

Chemical Composition and Cytotoxic Activity of the Essential Oil and Oleoresins of In Vitro Micropropagated Ansellia africana Lindl: A Vulnerable Medicinal Orchid of Africa.

Orchids are rich treasure troves of various important phytomolecules. Among the various medicinal orchids, Ansellia africana stands out prominently in the preparing of various herbal medicines due to its high therapeutic importance. The nodal explants of A. africana were sampled from asymbiotically germinated seedlings on basal Murashige and Skoog (MS) medium and were micropropagated in MS medium supplemented with 3% sucrose and 10 µM meta topolin (mT) + 5 µM naphthalene acetic acid (NAA) +15 µM indole butyric acid (IBA) + 30 µM phloroglucinol (PG). In the present study, the essential oil was extracted by hydrodistillation and the oleoresins by the solvent extraction method from the micropropagated A. africana. The essential oil and the oleoresins were analysed by Gas Chromatography (GC) and GC/MS (Mass spectrometry). A total of 84 compounds were identified. The most predominant components among them were linoleic acid (18.42%), l-ascorbyl 2,6-dipalmitate (11.50%), linolenic acid (10.98%) and p-cresol (9.99%) in the essential oil; and eicosane (26.34%), n-butyl acetate (21.13%), heptadecane (16.48%) and 2-pentanone, 4-hydroxy-4-methyl (11.13%) were detected in the acetone extract; heptadecane (9.40%), heneicosane (9.45%), eicosane (6.40%), n-butyl acetate (14.34%) and styrene (22.20%) were identified and quantified in the ethyl acetate extract. The cytotoxic activity of essential oil and oleoresins of micropropagated A. africana was evaluated by MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium Bromide) assay on Vero cells compared to the standard drug doxorubicin chloride. The present research contains primary information about the therapeutic utility of the essential oil and oleoresins of A. africana with a promising future research potential of qualitative and quantitative improvement through synchronised use of biotechnological techniques.

Biotrickling filter modeling for styrene abatement. Part 2: Simulating a two-phase partitioning bioreactor.

A dynamic model describing styrene abatement was developed for a two-phase partitioning bioreactor operated as a biotrickling filter (TPPB-BTF). The model was built as a coupled set of two different systems of partial differential equations depending on whether an irrigation or a non-irrigation period was simulated. The maximum growth rate was previously calibrated from a conventional BTF treating styrene (Part 1). The model was extended to simulate the TPPB-BTF based on the hypothesis that the main change associated with the non-aqueous phase is the modification of the pollutant properties in the liquid phase. The three phases considered were gas, a water-silicone liquid mixture, and biofilm. The selected calibration parameters were related to the physical properties of styrene: Henry's law constant, diffusivity, and the gas-liquid mass transfer coefficient. A sensitivity analysis revealed that Henry's law constant was the most sensitive parameter. The model was successfully calibrated with a goodness of fit of 0.94. It satisfactorily simulated the performance of the TPPB-BTF at styrene loads ranging from 13 to 77 g C m-3 h-1 and empty bed residence times of 30-15 s with the mass transfer enhanced by a factor of 1.6. The model was validated with data obtained in a TPPB-BTF removing styrene continuously. The experimental outlet emissions associated to oscillating inlet concentrations were satisfactorily predicted by using the calibrated parameters. Model simulations demonstrated the potential improvement of the mass-transfer performance of a conventional BTF degrading styrene by adding silicone oil.

Biotrickling filter modeling for styrene abatement. Part 1: Model development, calibration and validation on an industrial scale.

A three-phase dynamic mathematical model based on mass balances describing the main processes in biotrickling filtration: convection, mass transfer, diffusion, and biodegradation was calibrated and validated for the simulation of an industrial styrene-degrading biotrickling filter. The model considered the key features of the industrial operation of biotrickling filters: variable conditions of loading and intermittent irrigation. These features were included in the model switching from the mathematical description of periods with and without irrigation. Model equations were based on the mass balances describing the main processes in biotrickling filtration: convection, mass transfer, diffusion, and biodegradation. The model was calibrated with steady-state data from a laboratory biotrickling filter treating inlet loads at 13-74 g C m-3 h-1 and at empty bed residence time of 30-15 s. The model predicted the dynamic emission in the outlet of the biotrickling filter, simulating the small peaks of concentration occurring during irrigation. The validation of the model was performed using data from a pilot on-site biotrickling filter treating styrene installed in a fiber-reinforced facility. The model predicted the performance of the biotrickling filter working under high-oscillating emissions at an inlet load in a range of 5-23 g C m-3 h-1 and at an empty bed residence time of 31 s for more than 50 days, with a goodness of fit of 0.84.

Comparing in situ removal strategies for improving styrene bioproduction.

As an important conventional monomer compound, the biological production of styrene carries significant promise with respect to creating novel sustainable materials. Since end-product toxicity presently limits styrene production by previously engineered Escherichia coli, in situ product removal by both solvent extraction and gas stripping were explored as process-based strategies for circumventing its inhibitory effects. In solvent extraction, the addition of bis(2-ethylhexyl)phthalate offered the greatest productivity enhancement, allowing net volumetric production of 836 ± 64 mg/L to be reached, representing a 320 % improvement over single-phase cultures. Gas stripping rates, meanwhile, were controlled by rates of bioreactor agitation and, to a greater extent, aeration. A periodic gas stripping protocol ultimately enabled up to 561 ± 15 mg/L styrene to be attained. Lastly, by relieving the effects of styrene toxicity, new insight was gained regarding subsequent factors limiting its biosynthesis in E. coli and strategies for future strain improvement are discussed.

Co-recycling of acrylonitrile-butadiene-styrene waste plastic and nonmetal particles from waste printed circuit boards to manufacture reproduction composites.

This study investigated the feasibility of using acrylonitrile-butadiene-styrene (ABS) waste plastic and nonmetal particles from waste printed circuit boards (WPCB) to manufacture reproduction composites (RC), with the aim of co-recycling these two waste resources. The composites were prepared in a twin-crew extruder and investigated by means of mechanical testing, in situ flexural observation, thermogravimatric analysis, and dimensional stability evaluation. The results showed that the presence of nonmetal particles significantly improved the mechanical properties and the physical performance of the RC. A loading of 30 wt% nonmetal particles could achieve a flexural strength of 72.6 MPa, a flexural modulus of 3.57 GPa, and an impact strength of 15.5 kJ/m2. Moreover, it was found that the application of maleic anhydride-grafted ABS as compatilizer could effectively promote the interfacial adhesion between the ABS plastic and the nonmetal particles. This research provides a novel method to reuse waste ABS and WPCB nonmetals for manufacturing high value-added product, which represents a promising way for waste recycling and resolving the environmental problem.

Enhanced styrene recovery from waste polystyrene pyrolysis using response surface methodology coupled with Box-Behnken design.

A work applied response surface methodology coupled with Box-Behnken design (RSM-BBD) has been developed to enhance styrene recovery from waste polystyrene (WPS) through pyrolysis. The relationship between styrene yield and three selected operating parameters (i.e., temperature, heating rate, and carrier gas flow rate) was investigated. A second order polynomial equation was successfully built to describe the process and predict styrene yield under the study conditions. The factors identified as statistically significant to styrene production were: temperature, with a quadratic effect; heating rate, with a linear effect; carrier gas flow rate, with a quadratic effect; interaction between temperature and carrier gas flow rate; and interaction between heating rate and carrier gas flow rate. The optimum conditions for the current system were determined to be at a temperature range of 470-505°C, a heating rate of 40°C/min, and a carrier gas flow rate range of 115-140mL/min. Under such conditions, 64.52% WPS was recovered as styrene, which was 12% more than the highest reported yield for reactors of similar size. It is concluded that RSM-BBD is an effective approach for yield optimization of styrene recovery from WPS pyrolysis.

Ultrasonic degradation of butadiene, styrene and their copolymers.

Ultrasonic degradation of commercially important polymers, styrene-butadiene (SBR) rubber, acrylonitrile-butadiene (NBR) rubber, styrene-acrylonitrile (SAN), polybutadiene rubber and polystyrene were investigated. The molecular weight distributions were measured using gel permeation chromatography (GPC). A model based on continuous distribution kinetics approach was used to study the time evolution of molecular weight distribution for these polymers during degradation. The effect of solvent properties and ultrasound intensity on the degradation of SBR rubber was investigated using different pure solvents and mixed solvents of varying volatility and different ultrasonic intensities.

Metal-organic framework MIL-101(Cr) for high-performance liquid chromatographic separation of substituted aromatics.

The diverse structures and pore topologies, accessible cages and tunnels, and high surface areas make metal-organic frameworks attractive as novel media in separation sciences. Here we report the slurry-packed MIL-101(Cr) column for high-performance liquid chromatographic separation of substituted aromatics. The MIL-101(Cr) packed column (5 cm long × 4.6 mm i.d.) offered high-resolution separation of ethylbenzene (EB) and xylene, dichlorobenzene and chlorotoluene isomers, and EB and styrene. The typical impurities of toluene and o-xylene in EB and styrene mixtures were also efficiently separated on the MIL-101(Cr) packed column. The column efficiencies for EB, m-dichlorobenzene, and m-chlorotoluene are 20000, 13000, and 10000 plates m(-1), respectively. The relative standard deviation for five replicate separations of the substituted aromatics was 0.2-0.7%, 0.9-2.9%, 0.5-2.1%, and 0.6-2.7% for the retention time, peak area, peak height, and half peak width, respectively. The MIL-101(Cr) offered high affinity for the ortho-isomer, allowing fast and selective separation of the ortho-isomer from the other isomers within 3 min using dichloromethane as the mobile phase. The effects of the mobile phase composition, injected sample mass, and temperature were investigated. The separation of xylene, dichlorobenzene, and chlorotoluene on MIL-101(Cr) was controlled by entropy change, while the separation of EB and styrene on MIL-101(Cr) was governed by enthalpy change.

Styrene removal from polluted air in one and two-liquid phase biotrickling filter: steady and transient-state performance and pressure drop control.

A Sporothrix variecibatus-inoculated biotrickling filter (BTF) was examined for styrene removal, without and with the addition of silicone oil, at different empty bed residence times. The highest elimination capacities (ECs) were 172.8 (without silicone oil) and 670 g m(-3)h(-1) (with silicone oil), respectively, corresponding to a 4-fold improvement in presence of oil. The addition of silicone oil formed a well-coalesced emulsion of fungi and silicone oil, resulting in filter-bed clogging. Clogging prevention strategies adopted were; (i) lowering the volume ratio of silicone oil from 10% to 2% (v/v), and (ii) periodic increase in trickling rate of the medium from 50 to 190 mL min(-1). During shock-load experiments, the BTF with silicone oil (2% v/v) could withstand high styrene loads, of up to 1900 g m(-3)h(-1), when compared to the BTF without silicone oil (400 g m(-3)h(-1)).

Application of a hybrid system comprising carbon-doped TiO2 film and a ceramic media-packed biofilter for enhanced removal of gaseous styrene.

It is difficult to efficiently remove gaseous styrene using a TiO(2) film-coated photoreactor under UV light. Therefore, we used a hybrid system consisting of a carbon-doped TiO(2) (C-TiO(2)) film and a media-packed biofilter in order to enhance the removal efficiency (RE) of gaseous styrene compared to that of a pure (undoped) TiO(2) photoreactor. The C-TiO(2) was synthesized by a sol-gel combustion method, and its absorption spectrum was stronger that of pure (undoped) TiO(2) in the UV-vis range. The resultant RE of the C-TiO(2) film was 113-200% higher than that of the pure TiO(2) film. The initial RE of the photoreactor for input styrene concentrations of 630 mg m(-3), 420 mg m(-3), and 105 mg m(-3) was 20.6%, 29.8%, and 40.0%, respectively. When the biofilter was added, the RE increased to 93.3%, 97.9%, and 99.0%, respectively. Thus, application of the hybrid system consisting of both a photoreactor coated with a C-TiO(2) film and a biofilter is advantageous in terms of the removal efficiency of gaseous styrene.

Biofiltration of mixtures of gas-phase styrene and acetone with the fungus Sporothrix variecibatus.

The biodegradation performance of a biofilter, inoculated with the fungus Sporothrix variecibatus, to treat gas-phase styrene and acetone mixtures under steady-state and transient conditions was evaluated. Experiments were carried out by varying the gas-flow rates (0.05-0.4m(3)h(-1)), leading to empty bed residence times as low as 17.1s, and by changing the concentrations of gas-phase styrene (0.01-6.3 g m(-3)) and acetone (0.01-8.9 g m(-3)). The total elimination capacities were as high as 360 g m(-3)h(-1), with nearly 97.5% removal of styrene and 75.6% for acetone. The biodegradation of acetone was inhibited by the presence of styrene, while styrene removal was affected only slightly by the presence of acetone. During transient-state experiments, increasing the overall pollutant load by almost 3-fold, i.e., from 220 to 600 g m(-3)h(-1), resulted in a sudden drop of removal efficiency (>90-70%), but still high elimination capacities were maintained. Periodic microscopic observations revealed that the originally inoculated Sporothrix sp. remained present in the reactor and actively dominant in the biofilm.

Complexation behavior of mono- and disaccharides by the vinylbenzeneboronic acid-divinylbenzene copolymer resins packed in a high-performance liquid chromatographic column.

Using an HPLC column packed with monodispersed vinylbenzeneboronic acid-divinylbenzene (V-D) copolymer resins, the elution behaviors of the mono- and disaccharides were studied under different pH mobile phases. The monodispersed V-D copolymer resins were prepared by the copolymerization of 4-vinylbenzeneboronic acid and divinylbenzene in the presence of template silica gel particles (particle size: 5 microm; pore size: 10 nm), followed by dissolution of the template silica gel using a NaOH solution. Similarly, styrene-divinylbenzene (S-D) copolymer resins as the control resins were also synthesized. The transmission electron micrographs of these polymer resins revealed a good monodispersity. The complexation behavior of the saccharides was evaluated by comparison of the peak area eluted through the V-D column for that through the S-D column. Four aldopentoses (D-ribose, D-arabinose, D-xylose, and D-lyxose) and four aldohexoses (D-glucose, D-mannose, D-galactose, and D-talose) were retained completely at pH 11.9. Especially, ribose and talose were totally retained even under acidic and neutral conditions. For the disaccharides, unlike sucrose and maltose, palatinose was completely retained in basic mobile phases.

Performance of a biofilter for the removal of high concentrations of styrene under steady and non-steady state conditions.

The performance of a laboratory scale perlite biofilter inoculated with a mixed culture was evaluated for gas phase styrene removal under various operating conditions. Experiments were carried out by subjecting the biofilter to different flow rates (0.15-0.9 m(3)h(-1)) and concentrations (0.03-17.3 gm(-3)), corresponding to inlet loading rates varying from as low as 3 gm(-3)h(-1) to as high as 1390 gm(-3)h(-1). A maximum elimination capacity (EC) of 382 gm(-3)h(-1) was achieved at an inlet loading rate of 464 gm(-3)h(-1) with a removal efficiency of 82%. The high elimination capacity reached with this system could have been due to the dominant presence of filamentous fungi among others. The impact of relative humidity (RH) (30%, 60% and >92%) on the biofilter performance was evaluated at two constant loading rates, viz., 80 and 260 gm(-3)h(-1), showing that inhibitory effects were only significant when combining the highest loads with the lowest relative humidities. Biomass distribution, moisture content and concentration profiles along the bed height were significantly dependent on the relative humidity of the inlet air and on the loading rate. The dynamic behaviour of the biofilter through vigorous short and long-term shock loads was tested at different process conditions. The biofilter was found to respond apace to rapid changes in loading conditions. The stability of the biomass within the reactor was apparent from the fast response of the biofilter to recuperate and handle intermittent shutdown and restart operations, either with or without nutrient addition.

Sorption of styrene from aqueous solutions with oil absorptive resin.

We demonstrated the utility of oil-absorbing 4-tert-butylstyrene-divinylbenzene-ethylene/propylene/diene resins in the removal of environmental hormones such as styrene from water. A maximum treatment efficiency of 99.47% was observed when using a static process, while the dynamic process yielded a maximum efficiency of 96.25%. The sorption efficiency was greater for solutions containing higher initial concentrations of styrene and for extended static contact times, but decreased with increasing hydraulic retention time. The influences of styrene concentration, sorption time, and hydraulic retention time on sorption efficiency were successfully predicted using a polynomial equation, sigmoidal function and exponential decay equation, respectively. It was found that the sorption process was well described by a first-order kinetic model.

Liquid-liquid extraction/headspace/gas chromatographic/mass spectrometric determination of benzene, toluene, ethylbenzene, (o-, m- and p-)xylene and styrene in olive oil using surfactant-coated carbon nanotubes as extractant.

BTEX-S compounds are widely distributed in the environment and can be present in different foodstuffs, including olive oil. Taking into account the risks of the exposure to these compounds, analytical methods for their determination in different matrices are mandatory. In this paper, the use of surfactant-coated multiwalled carbon nanotubes as additive in liquid-liquid extraction is applied for the determination of single-ring aromatic compounds in olive oil samples. After sample treatment, the aqueous extracts are subsequently analyzed by headspace/gas chromatography/mass spectrometry allowing the determination of BTEX-S within ca. 15 min. Each stage of the proposed LLE/HS/GC/MS configuration involves a selectivity enhancement avoiding the interference of other compounds of the sample matrix. Limits of detection were in the range 0.25 ng mL(-1) (obtained for ethylbenzene) and 0.43 ng mL(-1) (for benzene). The repeatability of the proposed method expressed as RSD varied between 1.9% (styrene) and 3.3% (benzene) (n=11).

Effect of admicellar properties on adsolubilization: column studies and solute transport.

Mixtures of anionic and cationic surfactants exhibit synergistic behavior as evidenced by low critical micelle concentrations (CMC) of the mixed system, increased surface activity, and improved detergency performance. The adsorption of a single-head anionic surfactant, sodium dodecyl sulfate (SDS), in mixture with a twin-head cationic surfactant, pentamethyl-octadecyl-1,3-propane diammonium dichloride (PODD), showed synergism of adsorption onto silica when present at a mixing ratio of 1:3 (cationic-rich), and also demonstrated lower surfactant desorption with water flushing of columns packed with the surfactant-modified media. In addition, the proportion of the mixed surfactants in the admicelles moved from the initial ratio of 1:3 towards equimolar after rinsing the surfactant-modified silica absorbent. The retardation of organic solutes passing through columns packed with modified-silica adsorbent increased nominally three fold for silica modified with mixed surfactants versus single surfactants (retardation factors increase from 4.0 to 12.8 for styrene and from 32.1 to 90.2 for ethylcyclohexane for single and mixed surfactants, respectively). Thus, this study demonstrates that mixed surfactant systems more effectively modified the silica surface than single surfactant systems both in terms of enhanced retardation of organic solutes and in terms of reduced surfactant desorption.

Preparation and evaluation of C18-bonded 1-microm silica particles for pressurized capillary electrochromatography.

Nonporous silica spheres (1 microm) were synthesized and bonded with octadecylsilane functionality. These stationary phase particles were packed electrokinetically into fused-silica capillaries with 100 microm id for a length of 20 cm, which was evaluated by using pressurized CEC (pCEC). The efficiency of the C18 RP column was characterized through the theoretical plates of thiourea, benzyl alcohol, toluene, styrene, and naphthalene. The effects of experimental parameters such as the applied voltage, sample size, pump flow rate, pH value and the concentration of the buffer solution, and the content of methanol in the mobile phase, on-column efficiency were evaluated. Column efficiency as high as 200 000 theoretical plates per meter for naphthalene was obtained with the optimal condition of 70% v/v methanol and 30% v/v of 10 mmol/L phosphate buffer (pH 7.8) at an applied voltage of 10 kV and a supplementary pressure of 500 psi.

Enhancement of styrene removal efficiency in biofilter by mixed cultures of Pseudomonas sp. SR-5.

The styrene-degrading bacterium Pseudomonas sp. SR-5 exhibited a high styrene removability in a biofilter. However, the styrene removal efficiency (RE) of SR-5 decreased with time. We carried out styrene gas removal in a biofilter inoculated with mixed cultures of SR-5 and other microorganisms to determine the possibility of obtaining an enhanced RE for a long period. The following three inocula were carried out: (i) styrene-degrading bacteria, strains 1 and 3, (ii) a benzoic acid-degrading bacterium Raoultella sp. A, and (iii) wastewater from a chemical company dealing with styrene. These biofilters with mixed SR-5 showed an enhanced RE compared with those with a single culture of SR-5. The complete styrene elimination capacities for ensuring 100% styrene removal in those mixed cultures were 151, 108 and 124 g/m(3)/h, compared with a single culture of SR-5.

Continuous spin fractionation and characterization by size-exclusion chromatography for styrene-butadiene block copolymers.

Linear and star-shaped styrene-butadiene block copolymers synthesized by anionic polymerization of butadiene and styrene were fractionated by applying a newly developed large-scale fractionation technique, named continuous spin fractionation (CSF). Their molecular weight and polydispersity index (d=M(w)/M(n)) were measured with size-exclusion chromatography and static light scattering. For the linear triblock copolymer a fractionation via temperature variation turned out to be better suited than the usual isothermal procedure. The star-shaped polymer with the d value of 1.33 was fractionated in two CSF steps to get the targeted sample, which has a considerably more uniform structure and a narrower molecular weight distribution (d=1.11). The corresponding starting linear diblock copolymer was fractionated in one step reducing d from 1.68 to 1.17. With one set of simple laboratory equipment, 1kg polymer can be fractionated per day. Utilizing CSF, for the first time, we fractionated successfully the block copolymers.