Toxicological risk assessment of bisphenol a released from dialyzers under simulated-use and exaggerated extraction conditions.

Bisphenol A (BPA) belongs to a group of chemicals used in the production of polycarbonate, polysulfone, and polyethersulfone which are used, among other applications, in the manufacture of dialyzers. While exposure to BPA is widespread in the general population, dialysis patients represent a population with potentially chronic parenteral BPA exposures. To assess the potential risk of BPA exposure to dialysis patients through dialyzer use, exposure estimates were calculated based on BPA levels measured by ultra-high performance liquid chromatography-quadrupole time-of-flight mass spectrometry following extractions from dialyzers manufactured by Fresenius Medical Care. Extraction conditions included both simulated-use leaching and exaggerated extractions to evaluate possible leachable and extractable BPA, respectively, from the devices. The mean BPA concentrations were 3.6 and 108.9 ppb from simulated-use and exaggerated extractions, respectively, from polycarbonate-containing dialyzers. No BPA was detected from polypropylene-containing dialyzers. Margins of Safety (MOS) were calculated to evaluate the level of risk to patients from estimated BPA exposure from the dialyzers, and the resulting MOS were 229 and 45 for simulated-use and exaggerated extractions, respectively. The findings suggest that there is an acceptable level of toxicological risk to dialysis patients exposed to BPA from use of the dialyzers tested in the current study.

Use of laser-induced breakdown spectroscopy for the determination of polycarbonate (PC) and acrylonitrile-butadiene-styrene (ABS) concentrations in PC/ABS plastics from e-waste.

Due to the continual increase in waste generated from electronic devices, the management of plastics, which represents between 10 and 30% by weight of waste electrical and electronic equipment (WEEE or e-waste), becomes indispensable in terms of environmental and economic impacts. Considering the importance of acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), and their blends in the electronics and other industries, this study presents a new application of laser-induced breakdown spectroscopy (LIBS) for the fast and direct determination of PC and ABS concentrations in blends of these plastics obtained from samples of e-waste. From the LIBS spectra acquired for the PC/ABS blend, multivariate calibration models were built using partial least squares (PLS) regression. In general, it was possible to infer that the relative errors between the theoretical or reference and predicted values for the spiked samples were lower than 10%.

Microwave-assisted surface modification for the separation of polycarbonate from polymethylmethacrylate and polyvinyl chloride waste plastics by flotation.

Microwave-assisted potassium permanganate modification (MPPM) was used for the flotation separation of polycarbonate (PC) from polyvinyl chloride (PVC) and polymethylmethacrylate (PMMA) waste plastics. The separation process was optimized by investigating the potassium permanganate concentration, treatment time, flotation time and frother concentration. MPPM selectively reduced the flotation recovery of PC. The optimum conditions were determined to be: potassium permanganate concentration, 2 mM/L; treatment time, 1 min; frother concentration, 17.57 g/L; and flotation time, 1 min. PC was efficiently separated from PVC and PMMA under the optimum conditions. The purity of the separated PC was 97.71%. The purity and recovery of PVC and PMMA were both >95%. The modification mechanism was investigated using the water contact angles, Fourier transform infrared spectrometry and scanning electron microscopy. This work provides technical insights into the industrial recycling of waste plastics.

Ammonia modification for flotation separation of polycarbonate and polystyrene waste plastics.

A promising method, ammonia modification, was developed for flotation separation of polycarbonate (PC) and polystyrene (PS) waste plastics. Ammonia modification has little effect on flotation behavior of PS, while it changes significantly that of PC. The PC recovery in the floated product drops from 100% to 3.17% when modification time is 13min and then rises to 100% after longer modification. The mechanism of ammonia modification was studied by contact angle, and Fourier transform infrared (FT-IR) and X-ray photoelectron spectroscopy (XPS) measurements. Contact angle of PC indicates the decline of PC recovery in the floated product is ascribed to an increase in surface wettability. FT-IR and XPS spectra suggest that ammonia modification causes chemical reactions occurred on PC surface. Flotation behavior of ammonia-modified PC and PS was investigated with respect to flotation time, frother concentration and particle sizes. Flotation separation of PC and PS waste plastics was conducted based on the flotation behavior of single plastic. PC and PS mixtures with different particle sizes are separated efficiently, implying that the technology possesses superior applicability to particle sizes of plastics. The purity of PS and PC is up to 99.53% and 98.21%, respectively, and the recovery of PS and PC is larger than 92.06%. A reliable, cheap and effective process is proposed for separation of PC and PS waste plastics.

Investigation on an innovative technology for wet separation of plastic wastes.

This paper presents an original device for the separation of plastic polymers from mixtures. Due to the combination of a characteristic flow pattern developing within the apparatus and density, shape and size differences among two or more polymers, this device allows their separation into two products, one collected within the instrument and the other one expelled through its outlet ducts. Experimental tests have been conducted to investigate the effectiveness of the apparatus, using two geometric arrangements, nine hydraulic configurations and three selections of polymers at three stages of a material life cycle. Tests with samples composed of a single typology of polymer have been used to understand the interaction between the particles and the carrying fluid within the apparatus in different hydraulic configurations and geometric arrangements. Multi-material tests are essential to simulate the real conditions in an industrial recycling plant. The separation results have been evaluated in terms of grade and recovery of a useful material. Under the proper hydraulic configurations, the experimentation showed that it is possible to produce an almost pure concentrate of Polyethylene Terephthalate (PET) from a mixture of 85% PET and 15% Polycarbonate (PC) (concentrate grade and recovery equal to 99.5% and 95.1%) and a mixture of 85% PET and 15% Polyvinyl Chloride (PVC) (concentrate grade and recovery equal to 97.9% and 100.0%). It is further demonstrated that almost pure concentrates of PVC and PC can be produced from a mixture of 85% PVC and 15% PC (PVC grade and recovery equal to 99.9% and 99.7%) and a mixture of 85% PC and 15% PVC (PC grade and recovery equal to 99.0% and 99.5%).

UHPLC-high-resolution mass spectrometry determination of bisphenol A and plastic additives released by polycarbonate tableware: influence of ageing and surface damage.

A new UHPLC-ESI-Orbitrap method for the identification and the quantitative determination of bisphenol A and some common additives employed in plastic manufacturing has been developed and validated. The method has been applied to evaluate the migration from 14 samples of tableware of different age and degree of surface damage, in both ethanol and isooctane (used as food simulants according to EU plastic regulation). Bisphenol A, three UV light absorbers, and one whitening agent were detected and quantified. Data were analyzed with the aim of exploring a possible correlation between bisphenol A and additives release, ageing, and surface integrity. A high correlation between age of samples, surface damage, and bisphenol A migration has been evaluated, while the release of additives was not correlated with other parameters. Obtained data showed for the first time that the release of bisphenol A seems to be more connected to ageing than to scratches and cracks occurrence. Graphical Abstract Bisphenol A and additives released by polycarbonate tableware: influence of ageing and surface damage.

[Simultaneous determination of total specific migration limit of seven benzene polycarbonic acids and their derivatives in food simulants by high performance liquid chromatography-ultraviolet detection].

A novel method for simultaneous determination of total specific migration limits (SML (T)) of trimellitic, isophthalic, terephthalic, phthalic acid and their derivatives (1, 2, 4-benzenetricarboxylic anhydride, isophthaloyl chloride and terephthaloyl chloride) in food simulants (10% (v/v) ethanol, 20% (v/v) ethanol, 50% (v/v) ethanol, 3% (w/v) acetic acid and olive oil) was developed by high performance liquid chromatography-ultraviolet detection (HPLC-UV). After the migration test, the soaking solution was cooled down and vortexed. After the extraction of olive oil food simulants with 0. 1% (w/v) ammonium acetate aqueous solution, the clear aqueous solution or other aqueous food simulants was filtered through a hydrophilic polytetrafluoroethylene filter with a disposable syringe before injection. The Synergi Polar-RP column (250 mm x 4.6 mm, 4 µm) and gradient elution mode were selected. The variable wavelength detector was set at 232 nm. The limits of quantification were 0.1-0.2 mg/kg; the linearity of the method was good with r2 > 0.999 91 over the range from 0.5 to 12 mg/L for aqueous food simulants or 0.5 to 12 mg/kg for olive oil food simulants. The recoveries of them were between 94. 3% and 105% with the relative standard deviations between 0.1% and 2.3% at the levels of 1.25, 2.50, 6.25 mg/kg. The method shows the low limits of detection, good recoveries and accuracies, and meets the requirement of ( EU) No 10/2011 regulation for the total specific migration limits of trimellitic, isophthalic, terephthalic, phthalic acids and their derivatives. The method has been applied to the analysis of food contact material samples.

Protein release from dihydroxyacetone-based poly(carbonate ester) matrices.

The release of therapeutics from solid polymer matrices is an important field of study in the area of controlled release. Here we report on the hydrolytic degradation of directly compressed discs comprised of statistically random polycarbonate esters based on lactic acid and dihydroxyacetone. The controlled release of two model proteins, bovine serum albumin and lysozyme, was explored using two percentage loadings (5 and 10 wt.%). A first order release pattern and a trend for faster protein release with increasing dihydroxyacetone content were observed over a time period ranging from 2.5 to 70 days. To analyze the effects of the internal polymer matrix environment on protein stability the enzymatic activity of released lysozyme was monitored. The results show a high level of enzyme activity for the polycarbonate ester ratios with more dihydroxyacetone in the backbone and at least 50% activity over the first month of release from the co-polymer ratios with more lactic acid in the backbone. Modeling of the release kinetics using the Korsmeyer-Peppas model showed a high correlation, indicating that the release of protein is a complex mechanism controlled by protein diffusion through, and erosion of, the co-polymer matrix. The outcomes show that these polycarbonate esters may be useful materials for extended controlled release of proteins.

Properties and water sorption characteristics of spaghetti prepared using various dies.

Spaghetti was prepared using dies made of different materials. The surface was observed using digital and optical microscopes, and was rougher for the spaghettis prepared using the Teflon, polypropylene, polycarbonate, aluminum, and bronze dies in this order. The extrusion velocity when passing through the die was faster, the bulk density was higher, and the rupture strength was greater for the spaghetti having the smoother surface. The die material did not affect the gelatinization temperature. The water sorption curves in boiling water containing 0.5% (w/v) sodium chloride were also observed. The curves were expressed by an equation of the hyperbolic type except for the early stage of sorption in order to estimate the equilibrium amount of water sorbed based on the bone-dry sample. The momentarily-sorbed amount of water, which is a hypothetical quantity to characterize the initial water intake, was estimated by fitting the experimental points within 60 s. The amount was higher for the spaghetti having the rougher surface.

Comparison of migration from polyethersulphone and polycarbonate baby bottles.

This work presents two analytical methods developed for measuring three components of polyethersulphone (PES) and applying them to the migration testing of 30 baby bottles made of PES. The study also provides migration results under the same conditions for bisphenol A (BPA) from 40 polycarbonate baby bottles using a well-established method adapted to low concentrations. For PES bottles, migration of diphenyl sulphone (DPS), 4,4'-dichlorodiphenyl sulphone (DCPS) and 4,4'-dihydroxydiphenyl sulphone (DHPS; also known as bisphenol S) was carried out using two different analytical methods with detection limits of 0.1-0.3 µg/kg, and, therefore, much below their respective European Commission Directive 2002/72/EC legislative migration limits of 50-3000 µg/kg, respectively. In parallel, 40 bottles made of polycarbonate were analysed for the migration of BPA using a method validated at EU level and modified to give a lower detection limit of 0.1 µg/kg. Migration tests were conducted into the simulant for milk 50% EtOH (as per Commission Regulation No. 321/2011 of 1 April 2011) according to the test conditions from the guidelines on test conditions for articles in contact with foodstuffs (with a focus on kitchenware) prepared by the EU Reference Laboratory and its network of National Reference Laboratories. None of the 30 bottles made of PES released any detectable amounts of DCPS or DHPS and only two bottles released a very low amount of DPS of ~1 µg/kg in the milk food simulant compared to a regulatory limit of 3000 µg/kg. For PC bottles, 32 bottles of 40 (80%) did not release BPA above the LOD of 0.1 µg/kg (in any of the three migration tests performed on each bottle). The other 20% of bottles exhibited only very minor migration, where the highest level in the first migration test was 1.83 µg/kg and most bottles did not release detectable BPA in the second and third test. Only one bottle, with a migration level of 1.08 µg/kg, in the first test still showed a detectable level in the last migration test (i.e. 0.42 µg/kg). It is important to note that the legal limit (European Commission Directive 2002/72/EC) was still 600 µg/kg for polycarbonate bottles at the time of purchase, preceding the precautionary ban taking effect from 1 June 2011 (Commission Directive 2011/8/EU; Commission Regulation No. 321/2011). This confirms that the likelihood of migration of BPA is very low and remains at very minute amounts. The results also suggest the absence of release from PES bottles based on the set of bottles investigated.

Migration of bisphenol A from plastic baby bottles, baby bottle liners and reusable polycarbonate drinking bottles.

Human exposure to bisphenol A (BPA) has recently received special attention. It has been shown that exposure to BPA may occur through the consumption of beverages or foods that have been in contact with polycarbonate (PC) plastic containers or epoxy resins in food packaging. A BPA migration study was conducted using a variety of plastic containers, including polycarbonate baby bottles, non-PC baby bottles, baby bottle liners, and reusable PC drinking bottles. Water was used to simulate migration into aqueous and acidic foods; 10% ethanol solution to simulate migration to low- and high-alcoholic foods; and 50% ethanol solution to simulate migration to fatty foods. By combining solid-phase extraction, BPA derivatization and analysis by GC-EI/MS/MS, a very low detection limit at the ng l(-1) level was obtained. Migration of BPA at 40 degrees C ranged from 0.11 microg l(-1) in water incubated for 8 h to 2.39 microg l(-1) in 50% ethanol incubated for 240 h. Residual BPA leaching from PC bottles increased with temperature and incubation time. In comparison with the migration observed from PC bottles, non-PC baby bottles and baby bottle liners showed only trace levels of BPA. Tests for leachable lead and cadmium were also conducted on glass baby bottles since these represent a potential alternative to plastic bottles. No detectable lead or cadmium was found to leach from the glass. This study indicated that non-PC plastic baby bottles, baby bottle liners and glass baby bottles might be good alternatives for polycarbonate bottles.

Retrieval analysis of a polycarbonate-urethane acetabular cup: a case report.

An acetabular cup made of a compliant polycarbonate-urethane material has been introduced as an alternative bearing solution. This case study examines the use of this acetabular cup in a single patient at 12 months. The cup had minimal loss of thickness with the most being in the superior area (approximately 10%) and minimal loss of weight (2.4%). On the back side was evidence of abrasive macroscopic wear on one side of the implanted component in the area of directional loading from the head to the acetabulum. On the front side, the wear rate was determined to be minimal (less than 15 mm3 per year), meaning that most of the change in thickness and weight was caused on the back side. The retrieved synovial fluid appeared normal in color and volume at the time of revision. The histology of the tissue taken showed minimal wear particles and minimal reactivity, confirming that the patient did not have any signs of synovitis.The analysis of the cup confirms the preclinically determined low wear articulation and biocompatibility of polycarbonate-urethane as a weight-bearing material. In summary, the surgical findings, data reviewed, and images taken from this case report warrant further study.

Explantation and analysis of the first retrieved human acetabular cup made of polycarbonate urethane: a case report.

This report describes the first human retrieval of a polycarbonate-urethane (PCU) acetabular cup implanted for 10.5 months that was revised for pain of unknown origin. By using a micro-CT analysis, the articulating surface was determined to have a wear rate of less than 1.4 mm3 per year. An analysis of the synovial fluid retrieved at the time of revision found an average particle size of 1 mum diameter. Overall, the surgical findings and analysis were consistent with the results observed in laboratory and animal studies. The histology and synovial fluid analysis found sparse evidence of particulate debris and no synovitis, indicating the potential of this articulating material for use as a bearing surface.

Sign constraints improve the detection of differences between complex spectral data sets: LC-IR as an example.

Spectroscopy is a fast and rich analytical tool. On many occasions, spectra are acquired of two or more sets of samples that differ only slightly. These data sets then need to be compared and analyzed, but sometimes it is difficult to find the differences. We present a simple and effective method that detects and extracts new spectral features in a spectrum coming from one set with respect to spectra of another set on the basis of the fact that these new spectral features are essentially positive quantities. The proposed procedure (i) characterizes the spectra of the reference set by a component model and (ii) uses asymmetric least squares (ASLS) to find differences with respect to this component model. It should be stressed that the method only focuses on new features and does not trace relative changes of spectral features that occur in both sets of spectra. A comparison is made with the conventional ordinary least squares (OLS) approach. Both methods (OLS and ASLS) are illustrated with simulations and are tested for size-exclusion chromatography with infrared detection (SEC-IR) of mixtures of polymer standards. Both methods are able to provide information about new spectral features. It is shown that the ASLS-based procedure yields the best recovery of new features in the simulations and in the SEC-IR experiments. Band positions and band shapes of new spectral features are better retrieved with the ASLS than with the OLS method, even those which could hardly be detected visually. Depending on the spectroscopic technique used, the ASLS-based method facilitates identification of the new chemical compounds.

The human macrophage response during differentiation and biodegradation on polycarbonate-based polyurethanes: dependence on hard segment chemistry.

Human monocytes, isolated from whole blood, were seeded onto tissue culture grade polystyrene (PS) and three polycarbonate-based polyurethanes (PCNUs) (synthesized with either 1,6-hexane diisocyanate (HDI) or 4,4'-methylene bis-phenyl diisocyanate (MDI), poly(1,6-hexyl 1,2-ethyl carbonate) diol (PCN) and 1,4-butanediol (BD) in different stoichiometric ratios (HDI:PCN:BD 4:3:1 or 3:2:1 and MDI:PCN:BD 3:2:1) (referred to as HDI431, HDI321 and MDI321, respectively). Following their differentiation to monocyte-derived macrophages (MDMs) the cells were trypsinized and reseeded onto each of the PCNUs synthesized with either 14C-HDI or 14C-BD and degradation was measured by radiolabel release (RR). When the differentiation surface was MDI321, there was more RR from 14C-HDI431 than from any other surface (p < 0.0001) whereas the amount of esterase (identified by immunoblotting) as well as the esterase activity was the greatest in MDM differentiated on PS, reseeded on 14C-HDI431 (p < 0.0001). The effect of potential degradation products (methylene dianiline (MDA) and BD) from the PCNUs was carried out to determine possible links between products and substrate-induced activation of MDM. MDA was found to inhibit RR 60% from MDM seeded on 14C-MDI321B (p < 0.0001), approximately 20% from 14C-HDI431 (p = 0.002) and no effect from 14C-HDI321B. MDA inhibited esterase activity 30% from MDM only on 14C-MDI321B (p = 0.003), but no effect on esterase activity was observed for the other two polymers. BD had no inhibitory effect on RR from any PCNU, but did inhibit esterase activity in MDM on 14C-HDI431 (p = 0.025). This study indicates that the degradation of a specific material is a multi-factorial process, dictated by its susceptibility to hydrolysis, the effect of specific products generated during this course of action, and perhaps not as well appreciated, the material's inherent ability to influence enzyme synthesis and release.

Confocal Raman microspectrometry: a vectorial electromagnetic treatment of the light focused and collected through a planar interface and its application to the study of a thin coating.

In-depth confocal Raman microspectrometry (CRM) studies through a planar interface between materials of mismatched refraction indices are known to be affected by a decrease of both the collected Raman intensity and the axial resolution as a function of the penetration depth. Following a previous model, which takes the refraction, diffraction, and spherical aberration effects into account when focusing a Gaussian incident laser beam with a high numerical aperture objective lens, a complete vectorial treatment of these phenomena is considered. It is demonstrated that off-axis refraction effects cannot be neglected and that the dimension of the confocal pinhole aperture plays a crucial role on the effective focal plane position and on the collection efficiency. We thus propose a more rigorous and complete approach to the problem, and we find a very good agreement between experimental and theoretical Raman intensity variations for a thick polyethylene sample as a function of the penetration depth. As compared with calculations where only refraction was considered, we confirm that the lengthening of the focus even for a large penetration depth is significantly reduced upon diffraction effects. As an illustrative example, the theoretical Raman responses for a thin coating of approximately 20 microns on a polymer substrate were investigated and compared to experimental results already published. Even though the interfacial region is spread over approximately 5-6 microns when using a 100x objective and a confocal pinhole of 200 microns diameter, it is definitively concluded that the apparent axial resolution is not drastically deteriorated with increasing depth and that the coating thickness may be directly estimated with a precision of approximately 1.0 micron (5%).

Airborne particles produced during enamel cleanup after removal of orthodontic appliances.

Airborne particles can be produced during enamel cleanup after the removal of fixed orthodontic appliances. Particles with an aerodynamic diameter of less than 2.5 microm, known as PM2.5, can reach the alveoli of the lungs. The aim of this experiment was to qualitatively determine whether such particles are produced during enamel cleanup at the end of orthodontic treatment. Particles were collected and examined under a scanning electron microscope. Aerodynamic diameters of the particles ranged from approximately 2 to 30 microm. X-ray analysis confirmed not only the presence of components of the adhesives being removed, but also tungsten from the bur and tooth enamel. In conclusion, inhalable particles can be produced during enamel cleanup at the completion of orthodontic treatment. Further investigation is required to determine the clinical significance of such particles, how their production can be minimized, and whether even smaller, fine or ultrafine, particles are produced.

[Improved method for determining bisphenol A in polycarbonate products without using dichloromethane].

An improved method for determination of bisphenol A (BPA), phenol (PH), p-tert-butylphenol (PTBP) and diphenylcarbonate (DPC) in polycarbonate products was developed without using the hazardous solvent dichloromethane. Polycarbonate samples were ground to powder or cut into small pieces, and 0.5 g was soaked in 5 mL of acetonitrile for 24 hours at 40 degrees C. The test solution was then filtered and subjected to HPLC analysis. The proposed method was evaluated by comparison of the results with those of the standard method for 14 polycarbonate products. Extraction ratios (average values obtained by the present method/average values obtained by the standard method) of BPA, PH, PTBP and DPC were 0.89-1.19, 0.89-1.14, 0.94-1.30 and 1.08-1.11, respectively. While 120 mL/sample of organic solvent is required in the standard method, only 5 mL/sample of acetonitrile was used in our new method.

Development of emission factors for polycarbonate processing.

Emission factors for selected volatile organic compounds (VOCs) and particulate emissions were developed while processing eight commercial grades of polycarbonate (PC) and one grade of a PC/acrylonitrile-butadiene-styrene (ABS) blend. A small commercial-type extruder was used, and the extrusion temperature was held constant at 304 degrees C. An emission factor was calculated for each substance measured and is reported as pounds released to the atmosphere/million pounds of polymer resin processed [ppm (wt/wt)]. Scaled to production volumes, these emission factors can be used by processors to estimate emission quantities from similar PC processing operations.

Change in the bisphenol A content in a polycarbonate orthodontic bracket and its leaching characteristics in water.

The change in the bisphenol A (BPA) content in a polycarbonate (PC) orthodontic bracket and its leaching characteristics were studied by immersing the bracket in water because BPA has been the matter of controversy in dentistry due to its estrogenic potential. PC brackets were placed in water at 37 degrees C and 60 degrees C and the BPA content in the bracket and the amount of BPA released into the water were analyzed at appropriate intervals by high performance liquid chromatography. The BPA content increased in the water with time and was 3.8-fold after 12 months at 37 degrees C and 12.4-fold after 14 weeks at 60 degrees C compared with the virgin value. The rate of BPA release also increased with time. The results suggested that BPA was released from the bracket time-dependently in the oral cavity. However, it was assessed that little or no estrogenic effect due to the released BPA is expected in the human body.