Search

Microplastics (MPs) pollution is a growing global concern due to its potential threat to human health, particularly concerning fetal health. Nevertheless, few studies have examined the sources of fetal MPs exposure and its impact on fetal development. In this study, MPs levels in maternal amniotic fluid (AF) and their associations with measures of fetal growth were investigated. Specifically, 40 human AF samples were collected to determine the presence and characteristics of MPs using laser direct infrared (LD-IR) spectroscopy. MPs were found in 32 out of 40 AF samples, with an average abundance of 2.01 ± 4.19 particles/g. Polyethylene (PE, 38.80 %) and chlorinated polyethylene (CPE, 26.98 %) were the most prevalent polymers. The majority of MPs (87.56 %) were 20-100 μm in size, and fragments (71.23 %) evidently prevailed in morphology. Additionally, a questionnaire was designed to explore the associations between MPs levels in the AF and maternal dietary habits, aiming at unveiling the potential sources of MPs in AF. The MPs levels in the AF were positively associated with the frequency of seafood consumption (r = 0.781, P < 0.001) and bottled water intake (r = 0.386, P = 0.014). Moreover, the associations between MPs levels in maternal AF and measures of fetal growth were evaluated. The abundance of total MPs in maternal AF were significantly negatively associated with gestational age (β = -0.44, 95 % CI, -0.83, -0.05). This study confirms the presence of MPs in human AF and provides compelling evidence linking them to gestational age, while highlighting the potential risks associated with dietary habits. These findings underscore the need for further investigation into the mechanisms of MPs transmission from mother to fetus and the potential health implications during fetal development, offering valuable insights for future policies aimed at safeguarding maternal and fetal health., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Marine debris pollution poses a significant global threat to biodiversity, with plastics being the primary debris type found in oceans due to their low-cost production and high demand worldwide. Microplastics (MPs, <5 mm in size) are highly bioavailable to a wide range of marine taxa, including marine mammals, through direct and indirect ingestion routes (i.e., trophic transfer). Recently, MP pollution has been detected on the Galapagos Marine Reserve, so in this study we developed a baseline framework for MP pollution in the Galapagos sea lion (GSL, Zalophus wollebaeki) through scat-based analysis. We collected 180 GSL scat samples from the southeast region following strict quality assurance/quality control protocols to detect, quantify and characterize physical-chemical properties of MPs through visual observations and μFT-IR spectroscopy. We recovered 81 MPs of varying sizes and colors in 37 % of samples (n = 66/180), consisting mostly of fibers (69 %, x¯ = 0.31 ± 0.57 particles scat -1 ). The number of particles per gram of sample wet weight ranged from 0.02 to 0.22 (x¯ = 0.04 ± 0.05 particles scat wet g -1 ). El Malecón and Punta Pitt rookeries at San Cristobal Island had the highest number of MPs (x¯ = 0.67 ± 0.51 and 0.43 ± 0.41 particles scat -1 , respectively), and blue-colored particles were the most common in all samples. We identified eleven polymers in 46 particles, consisting mostly of polypropylene-polyethylene copolymer, polypropylene, cellulose, polyethylene, and polyvinyl chloride. The textile, fishing, and packaging industries are likely significant sources of microfibers into this insular ecosystem. Our results suggest that the GSL is exposed to MPs due to anthropogenic contamination that is subsequently transferred through trophic processes. These findings provide an important baseline framework and insights for future research on MP pollution in the region, as well as for management actions that will contribute to the long-term conservation of the GSL., Competing Interests: Declaration of competing interest The authors declare no competing interests., (Copyright © 2023 Elsevier B.V. All rights reserved.)

The impact of microplastics (MPs, plastic particles ≤5 mm) on ecosystems is of great concern. Road surfaces represent a significant source of MPs where plastic fragments are physically and chemically reduced to MPs. However, the literature lacks information on fragmentation tendencies below 11 μm. This study aimed to characterize the occurrence of MPs in road dust in different size fractions down to 1.1 μm. Road dust was collected at five sites near a major road in Kusatsu city, Japan, and partitioned by size into 13 fractions (1.1-850 μm). The coarser fractions accounted for a greater proportion of the dust. The percentage of organic matter, determined by loss on ignition, increased as the fractions became finer. Pyrolysis-gas chromatography-mass spectrometry was used to quantify 12 types of polymers in each fraction. The dust was found to contain nine types of MP, namely, polyethylene (PE), polypropylene (PP), polyvinylchloride (PVC), polystyrene (PS), styrene/butadiene rubber (SBR), acrylonitrile/butadiene/styrene resin (ABS), polycarbonate (PC), polymethylmethacrylate (PMMA), and polyamide 66 (PA66). The total MP concentration in road dust particles by particle size fraction (concentration f ) began to increase from the 125-250 μm fraction and remained elevated in finer fractions down to 1.1 μm, indicating that MPs in the road dust micronized to at least 1.1 μm. However, for individual polymer types, the tendency for concentration f to increase or decrease with particle size fraction varied: the concentration f of some polymers, such as PE and PVC, remained elevated in fractions down to 1.1 μm; the concentration f of SBR, a rubber-MP, showed a stable or decreasing trend in fractions of 7.0-11 μm and finer. Particles of PE, PVC, and some other plastics might become increasingly finer, even down to 1.1 μm. Further research is needed to understand the comminution limits of these polymers under pertinent environmental conditions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier Ltd.. All rights reserved.)

Formamide has been classified as a Class 1B reproductive toxicant to children by the European Union (EU) Chemicals Agency. Foam mats are a potential source of formamide and ammonia. Online dopant-assisted atmospheric pressure photoionization time-of-flight mass spectrometry (DA-APPI-TOFMS) coupled with a Teflon environmental chamber was developed to assess the exposure risk of formamide and ammonia from foam mats to children. High levels of formamide (average 3363.72 mg/m 3 ) and ammonia (average 1586.78 mg/m 3 ) emissions were measured from 21 foam mats with three different raw material types: ethylene-vinyl acetate (EVA: n = 7), polyethylene (PE: n = 7), and cross-linked polyethylene (XPE: n = 7). The 28 day emission testing for the selected PE mat showed that the emissions of formamide were 2 orders of magnitude higher than the EU emission limit of 20 μg/m 3 , and formamide may be a permanent indoor contaminant for foam mat products during their life cycle. The exposure assessment of children aged 0.5-6 years showed that the exposure dose was approximately hundreds of mg/kg-day, and the age group of 0.5-2 years was subject to much higher dermal exposures than others. Thus, this study provided key relevant information for further studies on assessing children's exposure to indoor air pollution from foam mats.

Fruit peels are rich source of bioactive compounds such as polyphenols, flavonoids, and antioxidants but are often discarded as waste due to limited pharmaceutical and nutraceutical applications. This study aimed to valorise pomegranate and citrus fruit peel into green synthesised silver nanoparticles (AgNPs) in order to modify cellulose-based wrapping material for prospective food packaging applications and propose an alternate and sustainable approach to replace polyethene based food packaging material. Four different concentrations of AgNO 3 (0.5 mM, 1 mM, 2 mM, and 3 mM) were used for green synthesis of AgNPs from fruit peel bioactive, which were characterised followed by phytochemical analysis. Ultraviolet-Visible spectroscopy showed surface plasmon resonance at 420 nm, XRD analysis showed 2θ peak at 27.8°, 32.16°, 38.5°, 44.31°, 46.09°, 54.76°, 57.47°, 64.61° and 77.50° corresponding to (210), (122), (111), (200), (231), (142), (241), (220) and (311) plane of face centred cubic crystal structure of AgNPs. Fourier-transform infrared spectroscopy analysis of AgNPs green synthesised from pomegranate and kinnow peel extract showed a major peak at 3277, 1640 and 1250-1020 1/cm while a small peak at 2786 1/cm was observed in case of pomegranate peel extract which was negligible in AgNPs synthesized from kinnow peel extract. Particle sizes of AgNPs showed no statistically significant variance with p > 0.10 and thus, 2 mM was chosen for further experimentation and modification of cellulose based packaging material as it showed smallest average particle size. Zeta potential was observed to be nearly neutral with a partial negative strength due to presence of various phenolic compounds such as presence of gallic acid which was confirmed by ultrahigh performance liquid chromatography-photodiode array(UHPLC-PDA) detector. Thermal stability analysis of green synthesised AgNPs qualified the sterilisation conditions up to 100 °C. AgNPs green synthesized from both the peel extracts had higher polyphenolic content, antioxidant and radical scavenging activity as compared to peel extracts without treatment (p < 0.05). The cellulose based food grade packaging material was enrobed by green synthesised AgNPs. The characterisation of modified cellulose wrappers showed no significant difference in thickness of modified cellulose wrappers as compared with untreated cellulose wrapper (p > 0.42) while weight and grammage increased significantly in modified cellulose wrapper (p < 0.05). The colour values on CIE scale (L*, a* and b*) showed statistically significant increase in yellow and green colour (p < 0.05) for modified cellulose wrappers as compared to control wrapper. The oxygen permeability coefficient, water vapour permeability coefficient, water absorption capacity and water behaviour characteristics (water content, swelling degree and solubility) showed significant decrease (p < 0.05) for modified cellulose wrapper as compared to control wrapper. A uniform distribution and density of green synthesised AgNPs across cellulose wrapper matrix was observed through scanning electron microscopy (SEM) images with no significant aggregation, confirming successful enrobing and stable immobilisation of nanoparticles from cellulose matrix. A seven-day storage study of bread wrapped in modified and control cellulose wrappers showed delayed occurrence of microbial, yeast and mould count in bread packaged in modified cellulose wrappers and thus, resulting in shelf life extension of bread. The results are encouraging for the potential applications of modified cellulose wrappers to replace polyethene based food packaging., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

While atmospheric microplastics have attracted scientific attention as a significant source of microplastic contamination in the environment, studies in large population centers remain sparse. Here we present the first report on the occurrence and distribution of atmospheric microplastics in Mexico City (Latin America's second most densely populated city), collected using PM 10 and PM 2.5 active samplers at seven monitoring stations (urban, residential, and industrial) during the dry and wet seasons of 2020. The results showed that microplastics were detected in all of the samples examined, with mean microplastic concentrations (items m -3 ) of 0.205 ± 0.061 and 0.110 ± 0.055 in PM 10 and PM 2.5 , respectively. The spatial distribution of microplastics showed seasonal variation, with greater abundances in locations closer to industrial and urban centers. There was also a significant difference in microplastic concentrations in PM 10 and PM 2.5 between the dry and wet seasons. The mean PM 2.5 /PM 10 ratio was 0.576, implying that microplastics were partitioned more towards PM 2.5 than PM 10 in Mexico City. Fibers were the most prominent shape (>75 %), and blue was the most common color (>60 %). The size characteristics indicated microplastics of varying lengths, ranging from 39 to 5000 μm, with 66 % being <500 μm. Metal contaminants such as aluminum, iron, and titanium were detected using SEM-EDX on randomly selected microplastics. The microplastics were identified as cellophane, polyethylene, polyethylene terephthalate, polyamide, and cellulose (rayon) using ATR-FTIR spectral analysis. Our findings unravel the extent and characteristics of atmospheric microplastics in the Mexico City metropolitan area, which will aid future research to better understand their fate, transport, and potential health risks, demanding more investigations and close monitoring., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Nurdles, also known as plastic resin pellets, are now a major source of plastic pollution on beaches globally, thus it is important to elucidate their weathering patterns and environmental fates as well as the associated pollutants. In this study we collected nurdles from 24 sites in the coastal bend region of south Texas, covering areas from the near shore railway stations to the adjacent bays and barrier islands. The morphologies of nurdles and associated pollutants including polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), and mercury, were investigated. The results showed that the nurdles varied greatly in color, shape, polymer composition, and oxidation degree. More than 80 % of the nurdles were made with polyethylene, and the rest with polypropylene, polyester, polystyrene, polyethylene-vinyl acetate, and polyvinyl chloride based on Fourier Transform Infrared Spectroscopy (FTIR) analysis. PCBs were not detected on nurdles. PAHs and mercury on nurdles were detected at 12 % and 20 % of the sampling sites. The total concentrations of detectable PAHs ranged from 92.59 to 1787.23 ng/g-nurdle, and the detectable mercury concentrations ranged from 1.23 to 22.25 ng/g-nurdle. Although the concentrations of these pollutants were not at the acute toxic effect level, the presence of PAHs and mercury suggested the potential risk of pollutant exposure to marine organisms in ecosystems, given the fact that nurdles are persistent in the environment., Competing Interests: Declaration of competing interest The authors declare no conflict of interest., (Copyright © 2022 Elsevier B.V. All rights reserved.)

The incidence of eutrophication is increasing due to fertilizer abuse and global warming. Eutrophication can induce the proliferation of cyanobacteria such as Microcystis , which produces microcystins. Microcystins are toxic to specific organs such as the liver and the heart. Thus, monitoring of microcystins is strongly required to control drinking water and agricultural product qualities. However, microcystins could be adsorbed by plastic materials during sample storage and preparation, hindering accurate analysis. Therefore, the current study examined the recovery rate of microcystins from six plastics used for containers and eight plastics used for membrane filters. Among the six plastics used for containers, polyethylene terephthalate showed the best recovery rate (≥81.3%) for 48 h. However, polypropylene, polystyrene, and high- and low-density polyethylenes showed significant adsorption after exposure for 1 hr. For membrane materials, regenerated cellulose (≥99.3%) showed the highest recovery rate of microcystins, followed by polyvinylidene fluoride (≥94.1%) and polytetrafluoroethylene (≥95.7%). The adsorption of microcystins appeared to be strongly influenced by various molecular interactions, including hydrophobic interaction, hydrogen bonding, and electrostatic interaction. In addition, microcystins' functional residues seemed to be critical factors affecting their adsorption by plastic materials. The present study demonstrates that polyethylene terephthalate and regenerated cellulose membrane are suitable plastic materials for the analysis of microcystins.

Headspace-gas chromatography-ion mobility spectrometry (HS-GC-IMS) and chemometric methods were utilized to analyze changes in volatile organic compounds (VOCs) of yellow-fleshed peach by 1-methylcyclopropylene (1-MCP) treatment and modified atmosphere packaging (MAP). Meanwhile, the storage quality of yellow-fleshed peach at room temperature (25°C) was also studied. Yellow-fleshed peach was treated by four methods, namely, nanomaterial packaging (NA), 1-MCP fumigation and nanomaterial packaging (1-MCP-NA), polyethylene (PE) packaging, and 1-MCP fumigation with polyethylene packaging (1-MCP-PE). Changes in the decay rate, firmness, browning index, soluble solid content, and titratable acid of the fruit were then measured at room temperature at 1, 4 and 10 days of storage. Thirty-two VOCs, including terpenoids, alcohols, esters, aldehydes, and ketones, were identified. Seventeen VOCs were found to be significant with predictive variable important in the projection (VIP) > 1 and p < 0.05 by analysis of variance and orthogonal projection to latent structure discriminant analysis (OPLS-DA). After 10 days of storage, the browning index of 1-MCP-NA group was 51.7%, which was lower than the control fruit (PE, 76.7%). Compared with other three treatments, 1-MCP-NA showed the better ability to delay and inhibit decreases in ester and aldehyde contents, and the ethanol content was lowest in the samples treated by 1-MCP-NA during storage. Differences among treatment groups were distinguished by principal component analysis (PCA) and hierarchical clustering heat map. The results showed that 1-MCP-NA could well maintain the quality and flavor stability of yellow-fleshed peach, and it had a good application prospect in the postharvest preservation of yellow-fleshed peach. PRACTICAL APPLICATION: In this study, 1-methylcyclopropylene (1-MCP) combined with nanomaterial (NA) packaging (1-MCP-NA) proved to have a better fresh preservation effect. 1-MCP-NA showed better ability to delay and inhibit decreases in ester and aldehyde contents by HS-GC-IMS technique. It provided a new strategy for postharvest storage of yellow-fleshed peaches., (© 2022 Institute of Food Technologists®.)

In this paper, a process combining biodegradation and Fenton oxidation was proposed for the removal of polydiallyldimethylammonium chloride-acrylic-acrylamide-hydroxyethyl acrylate (PDM) in aqueous phase. Biodegradation of PDM was investigated in activated sludge systems, and the effects of the solution pH, mixed liquid suspended solids (MLSS), salinity, co-substrate, and initial substrate concentration, were studied. The biodegradation process was well-described with the Monod model and the values of the kinetics parameters v max , k s were 0.05 h -1 and 333 mg/L. The optimal biodegradation conditions in the experimental range were determined to be: pH = 7.0, 0%-0.01% (w/v) NaCl, 4000 mg/L of MLSS, and 500 mg/L of glucose as co-substrate. FT-IR analysis indicated that PDM molecules biodegradation partly. The microbial community structures and dehydrogenase activity analysis revealed that PDM showed some toxicity to microorganisms in activated sludge. The effects of several parameters, including the pH and chemical doses, were investigated for removing PDM in Fenton oxidation process. The optimal Fenton oxidation process conditions in the experimental range were pH = 2.0, Fe 2+ concentration of 40 mg/L, and H 2 O 2 dosage of 23 mL/L. PDM was treated by biodegradation and subsequent Fenton oxidation under the optimal operating conditions. The removal efficiency was 44.5% after the biodegradation process and further increased to 85.5% after Fenton oxidation. The combined process was revealed to be a promising solution for achieving effective and economical removal of PDM., (Copyright © 2019 Elsevier Inc. All rights reserved.)

Metal-on-metal (MoM) hip arthroplasties produce abundant implant-derived wear debris composed mainly of cobalt (Co) and chromium (Cr). Cobalt-chromium (Co-Cr) wear particles are difficult to identify histologically and need to be distinguished from other wear particle types and endogenous components (e.g., haemosiderin, fibrin) which may be present in MoM periprosthetic tissues. In this study we sought to determine whether histological stains that have an affinity for metals are useful in identifying Co-Cr wear debris in MoM periprosthetic tissues. Histological sections of periprosthetic tissue from 30 failed MoM hip arthroplasties were stained with haematoxylin-eosin (HE), Solochrome Cyanine (SC), Solochrome Azurine (SA) and Perls' Prussian Blue (PB). Sections of periprosthetic tissue from 10 cases of non-MoM arthroplasties using other implant biomaterials, including titanium, ceramic, polymethylmethacrylate (PMMA) and ultra-high molecular weight polyethylene (UHMWP) were similarly analysed. Sections of 10 cases of haemosiderin-containing knee tenosynovial giant cell tumour (TSGCT) were also stained with HE, SC, SA and PB. In MoM periprosthetic tissues, SC stained metal debris in phagocytic macrophages and in the superficial necrotic zone which exhibited little or no trichrome staining for fibrin. In non-MoM periprosthetic tissues, UHMWP, PMMA, ceramic and titanium particles were not stained by SC. Prussian Blue, but not SC or SA, stained haemosiderin deposits in MoM periprosthetic tissues and TSGT. Our findings show that SC staining (most likely Cr-associated) is useful in distinguishing Co-Cr wear particles from other metal/non-metal wear particles types in histological preparations of periprosthetic tissue and that SC reliably distinguishes haemosiderin from Co-Cr wear debris.

The cationic polyelectrolyte pDADMAC is widely used in biopharmaceutical industry as a flocculating agent to enhance clarification throughput and downstream filtration operations. Due to the possible toxicity, pDADMAC should be assessed for an acceptable residual level to ascertain the safety of the product to patients. The strong protein-polyelectrolyte interaction, however, can negatively affect sensitivity and accuracy of measurements. This paper reports on the application of size exclusion (SE) chromatography coupled to evaporative light scattering detector (ELSD) to the quantitative determination of pDADMAC in monoclonal antibody formulations and in process intermediates during downstream purification. The SE chromatography was performed under isocratic condition with a mobile phase consisting of 0.1% TFA in water (90%) and acetonitrile (10%) at a flow rate of 0.4 ml/min. A quantification limit (S/N = 10) of 0.85 ppm was achieved in sample matrix, which is sufficiently low for the trace analysis of this compound in protein-containing samples., (Copyright © 2018 International Alliance for Biological Standardization. Published by Elsevier Ltd. All rights reserved.)

Aseptic loosening is one of the main failure modes in artificial joints. Significant information about the aseptic loosening is carried by the wear debris of the joints. In this paper, the wear debris acquired from the ultrahigh molecular weight polyethylene (UHMWPE) artificial joints is prepared and a systematic research is carried out to investigate the wear mechanism of aseptic loosening using the wear debris analysis. The hip joint simulator was used to conduct the wear tests of the CoCrMo-UHMWPE artificial joint friction pairs. The scanning electron microscope (SEM) was employed to analyze the wear debris profiles. The analysis results demonstrated that the UHMWPE joints mainly produced the roundness, tuberous, lacerated, sheet, pole-liked and strip wear debris, and the wear mechanism of the joint aseptic loosening had a close relationship with the morphology of the debris types. The adhesive wear, fatigue wear and laceration under alternating stress were the main causes of the joint failure. Based on the wear debris analysis results, a new diagnosis method using the radar map fractal representation was proposed to diagnose the failure of the artificial joints.

Aim: To compare two different types of inserts: Ultra-high molecular weight polyethylene (UHMWPE) and cross-linked polyethylene with a quantitative and qualitative study of polyethylene wear particles in synovial fluid 3 years after total knee arthroplasty., Material and Methods: A prospective, randomized, controlled cohort study with blinded evaluation was carried out on 25 patients undergoing staged bilateral total knee replacement, 6 months apart. Knee arthrocentesis was performed on 12 patients 3 years after surgery, and the polyethylene particles were analyzed., Results: No significant differences were found in the number of particles generated by the two different types of inserts at 3 years from total knee arthroplasty (3,000×: x¯ cross-linked=849.7; x¯ UHMWPE=796.9; P=.63; 20,000×: x¯ cross-linked=66.3; x¯ UHMWPE=73.1; P=.76). Likewise, no differences in the probability of finding elongated (χ 2 =0.19; P=.66) or rounded (χ 2 =1.44; P=.23) particles in both types of inserts were observed. However, the probability of finding fibrillar particles is 3.08 times greater in UHMWPE., Conclusions: Cross-linked polyethylene does not significantly reduce the generation of polyethylene particles in patients with total knee arthroplasty, 3 years after the surgical procedure., (Copyright © 2018 SECOT. Publicado por Elsevier España, S.L.U. All rights reserved.)

Coefficient of friction (COF) tests were conducted on 28-mm and 36-mm-diameter hip joint prostheses for four different material combinations, with or without the presence of Ultra High Molecular Weight Polyethylene (UHMWPE) particles using a novel pendulum hip simulator. The effects of three micro dimpled arrays on femoral head against a polyethylene and a metallic cup were also investigated. Clearance played a vital role in the COF of ceramic on polyethylene and ceramic on ceramic artificial hip joints. Micro dimpled metallic femoral heads yielded higher COF against a polyethylene cup; however, with metal on metal prostheses the dimpled arrays significantly reduced the COF. In situ images revealed evidence that the dimple arrays enhanced film formation, which was the main mechanism that contributed to reduced friction., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

Purpose: Osteolysis in total hip arthroplasty (THA) depends on polyethylene wear and dictates the survival of the prosthesis. Dual mobility in THAs, which is claimed to reduce dislocation risk, has very good long-term clinical results. However, little is known about how the liner wears in this design, compared to the standard single mobility model., Methods: A comparative study looking at wear of a conventional ultra-high-molecular-weight polyethylene liner, using gravimetric measurement, between dual mobility implants and standard implants, was performed on a simulator in accordance with a normed protocol based on the same dimensions, environmental conditions and stresses. A linear regression test was employed., Results: Under the same conditions (loading, cycles, sterilization, material and surface roughness), the gravimetric wear (for conventional polyethylene) is comparable between a standard and a dual mobility cup. This correlates to ten year follow-up results of dual mobility cup., Discussion - Conclusion: This in vitro equivalent wear serves to confirm the very good long-term clinical results observed with dual mobility bearing, whose use should not be restricted by concerns about increased polyethylene wear.

The observation of tribological phenomena occurring in total knee replacement (TKR) simulators may be obscured by the intrinsic complexity of their operation: the dynamics and kinematics prescribed by the ISO 14243-3:2014 standard, and the geometry of the surfaces involved. On the other hand, evaluating the individual performance of the tribosystem elements may be carried out in simpler apparatuses. An experimental method is presented here, by means of which the arthrokinematics and loading conditions prescribed by the said standard are adapted to a ball-on-disc configuration in order to observe the behavior of the coefficient of friction along an entire walking cycle, using the contact point of an AISI 316L stainless steel ball rolling/sliding on an ultra-high molecular weight polyethylene (UHMWPE) disc, lubricated by a solution of fetal bovine serum, at 37°C. The method was tried on two different testing fluids prepared with protein concentrations of 20g/L, according to the said standard, and 36g/L, as received. The statistical model obtained for the behavior of the COF during the entire walking cycle may be used in numerical simulations of UHMWPE wear, under the conditions established by ISO 14243-3:2014., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Marine plastic debris are found worldwide in oceans and coastal areas. They degrade only slowly and contain chemicals added during manufacture or absorbed from the seawater. Therefore, they can pose a long-lasting contaminant source and potentially transfer chemicals to marine organisms when ingested. In order to assess their risk, the contaminant concentration in the plastics needs to be estimated and differences understood. We collected from literature plastic water partition coefficients of various organic chemicals for seven plastic types: polydimethylsiloxane (PDMS), high-density, low-density and ultra-high molecular weight polyethylene (LDPE, HDPE, UHMWPE), polystyrene (PS), polypropylene (PP), and polyvinyl chloride (PVC). Most data was available for PDMS (1060) and LDPE (220), but much less for the remaining plastics (73). Where possible, regression models were developed and the partitioning was compared between the different plastic types. The partitioning of chemicals follows the order of LDPE≈HDPE≥PP>PVC≈PS. Data describing the impact of weathering are urgently needed., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Microplastics are increasingly detected in the environment and the consequences on water resources and ecosystems are not clear to date. The present study provides a cost-effective and straightforward method to determine the mass concentrations of polymer types using thermal analysis. Characteristic endothermic phase transition temperatures were determined for seven plastic polymer types using TGA-DSC. Based on that, extracts from wastewater samples were analyzed. Results showed that among the studied polymers, only PE and PP could be clearly identified, while the phase transition signals of the other polymers largely overlap each other. Subsequently, calibration curves were run for PE and PP for qualitative measurements. 240 and 1540mg/m(3) of solid material (12µm to 1mm) was extracted from two wastewater effluent samples of a municipal WWTP of which 34% (81mg/m(3)) and 17% (257mg/m(3)) could be assigned to PE, while PP was not detected in any of the samples. The presented application of TGA-DSC provides a complementary or alternative method to FT-IR analyses for the determination of PE and PP in environmental samples., (Copyright © 2016 Elsevier B.V. All rights reserved.)

Ultrahigh molecular weight polyethylene (UHMWPE) has remained the primary polymer used in hip, knee and shoulder replacements for over 50 years. Recent case studies have demonstrated that catastrophic fatigue fracture of the polymer can severely limit device lifetime and are often associated with stress concentration (notches) integrated into the design. This study evaluates the influence of notch geometry on the fatigue of three formulations of UHMWPE that are in use today. A linear-elastic fracture mechanics approach is adopted to evaluate crack propagation as a function of notch root radius, heat treatment and Vitamin E additions. Specifically, a modified stress-intensity factor that accounts for notch geometry was utilized to model the crack driving force. The degree of notch plasticity for each material/notch combination was further evaluated using finite element methods. Experimental evaluation of crack speed as a function of stress intensity was conducted under cyclic tensile loading, taking crack length and notch plasticity into consideration. Results demonstrated that crack propagation in UHMWPE emanating from a notch was primarily affected by microstructural influences (cross-linking) rather than differences in notch geometry., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

In this work, two new types of polycyclic aromatic grafted polysiloxanes, namely, 3,4-bis(4-fluoro phenyl)-2,5-diphenyl polysiloxane (FPP) and 3,4-bis(3,4,5-trifluoro phenyl)-2,5-diphenyl polysiloxane (TFPP), were synthesized and statically coated onto capillary columns as stationary phases for gas chromatography (GC). Based on their McReynolds constants, both columns exhibited moderate polarity. The efficiencies of the FPP and TFPP columns were 3316 (k=3.96, naphthalene; 0.25mm inner diameter) and 3768 (k=4.14, naphthalene; 0.25mm inner diameter) plates/m, respectively. The thermostability of the polymers was tested by thermogravimetric analysis (TGA), and results revealed that both TFPP and FPP began to decompose slightly at 380°C. Separation of polyethylene pyrolysis products showed that the upper working temperature of the two columns can reach up to 360°C. Relying on their unique polarizable characteristics in combination with other types of interactions, such as H-bond acceptor, dipole-dipole, and dispersive interactions, the newly synthesized polarizable stationary phases offered unique selectivity for aromatic isomers and substituted benzenes. A slight separation difference between TPP and TFPP was observed. TFPP also exerted excellent selectivity for polycyclic aromatic hydrocarbons, fatty acid esters, and fatty alcohols. Overall, FPP and TFPP demonstrated considerable potential for further applications because of their unique structures and outstanding separation performance., (Copyright © 2016 Elsevier B.V. All rights reserved.)

A simple and rapid method was developed for the detection of poly(diallyldimethylammonium chloride) (PDADMAC) using citrate-capped silver nanoparticles (AgNPs). Detection was based on anti-aggregation of AgNPs in phosphate buffer caused by PDADMAC. Due to its positive charges, PDADMAC was adsorbed onto AgNPs via electrostatic interaction with citrate, which resulted in the charges at the particle surfaces to become positive and caused repulsion among particles. Furthermore, long-chain PDADMAC provided steric hindrance. These two effects promoted the dispersion of AgNPs in the phosphate buffer. A change in the state of dispersion influenced the surface plasmon resonance (SPR) of AgNPs. Therefore, in this work, the concentration of PDADMAC was determined by monitoring changes in absorbance (at 396 nm) caused by SPR of AgNPs. Under optimal conditions, the calibration was linear over the range of 1 to 100 mg L(-1) with a detection limit of 0.7 mg L(-1). Satisfactory precision was obtained (RSD = 2.8%). This method was successfully applied to the determination of PDADMAC in tap water samples. The recoveries ranged from 86.0 - 107.5%.

Microplastics (<5mm) have been discovered in fresh and saltwater ecosystems, sediments, and wastewater effluent around the world. Their ability to persist and accumulate up food chains should be a concern as research is still experimenting with techniques to assess their long-term effects on the environment. I sought to characterize the microbeads found in facial exfoliating cleansers so as to better understand how to reduce this source of pollution through consumer use and wastewater treatment solutions. By sampling products from national-grossing cosmetic personal care brands, I was able to gather information on the size, color, volume, mass, and concentration of polyethylene beads in the cleansers. From that data, I modeled onto a consumer survey the estimated volume of microplastics entering a wastewater stream. Through inquiry, I learned the practices of two local wastewater treatment facilities. My findings show that consumer decisions and treatment protocols both play crucial parts in minimizing microplastic pollution., (Copyright © 2015. Published by Elsevier Ltd.)

Understanding the transfer of chemicals between passive samplers and water is essential for their use as monitoring devices of organic contaminants in surface waters. By applying Fick's second law to diffusion through the polymer and an aqueous boundary layer, the authors derived a mathematical model for the uptake of chemicals into a passive sampler from water, in finite and infinite bath conditions. The finite bath model performed well when applied to laboratory observations of sorption into polyethylene (PE) sheets for various chemicals (polycyclic aromatic hydrocarbons, polychlorinated biphenyls [PCBs], and dichlorodiphenyltrichloroethane [DDT]) and at varying turbulence levels. The authors used the infinite bath model to infer fractional equilibration of PCB and DDT analytes in field-deployed PE, and the results were nearly identical to those obtained using the sampling rate model. However, further comparison of the model and the sampling rate model revealed that the exchange of chemicals was inconsistent with the sampling rate model for partially or fully membrane-controlled transfer, which would be expected in turbulent conditions or when targeting compounds with small polymer diffusivities and small partition coefficients (e.g., phenols, some pesticides, and others). The model can be applied to other polymers besides PE as well as other chemicals and in any transfer regime (membrane, mixed, or water boundary layer-controlled). Lastly, the authors illustrate practical applications of this model such as improving passive sampler design and understanding the kinetics of passive dosing experiments., (© 2015 SETAC.)

This paper describes a new efficient method for the processing of post-consumer polypropylene (and other polyolefins) wastes into polar waxes that have potential applications. This technology includes two key steps. In the first step, the post-consumer polyolefins are purified mostly from oil which is used as a solvent in processing of polyolefin wastes (like metalized polyolefin films), and in the second step, the oxidative degradation process is initiated to obtain polar waxes or, alternatively, the purified polymer can be granulated. The results of laboratory research on both steps are presented, as well as a comparison of the obtained granulates and polar waxes with commercially available products., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Waste management in Greece relies heavily on unsustainable waste practices (mainly landfills and in certain cases uncontrolled dumping of untreated waste). Even though major improvements have been achieved in the recycling of municipal solid waste during recent years, there are some barriers that hinder the achievement of high recycling rates. Source separation of municipal solid waste has been recognised as a promising solution to produce high-quality recycled materials that can be easily directed to secondary materials markets. This article presents an innovative miniature waste separator/compressor that has been designed and developed for the source separation of municipal solid waste at a household level. The design of the system is in line with the Waste Framework Directive (2008/98/EC), since it allows for the separate collection (and compression) of municipal solid waste, namely: plastic (polyethylene terephthalate and high-density polyethylene), paper (cardboard and Tetrapak) and metal (aluminium and tin cans). It has been designed through the use of suitable software tools (LS-DYNA, INVENTROR and COMSOL). The results from the simulations, as well as the whole design process and philosophy, are discussed in this article., (© The Author(s) 2015.)

Biota-sediment accumulation factors (BSAF), frequently used to predict tissue concentrations of organisms living within and above sediments contaminated with hydrophobic organic chemicals, often produce inaccurate estimates. Hence, freely dissolved porewater concentrations, CW , have also been investigated as predictors of organism tissue concentrations, but they are more difficult to measure than bulk sediment concentrations (used with BSAF). In situ passive sampling methods, however, make it possible to deduce CW with less effort than required to measure the value directly and make it possible to relate CW with tissue concentrations of undisturbed, native organisms. In the present study, polyethylene passive samplers containing performance reference compounds (d10-phenanthrene, d10-pyrene, and d12-chrysene) were deployed in diverse sediment beds near Boston, Massachusetts, USA, for a 1-wk period. Clams (Mya arenaria) and sediments were then collected from the deployed sediment beds. Concentrations of 3 polycyclic aromatic hydrocarbons (PAHs; phenanthrene, pyrene, and chrysene) were measured in the porewaters, in clam tissues, and in the bulk sediment. Biota-sediment accumulation factors and polyethylene-deduced CW were used to predict organism tissue concentrations. Ratios of predicted-to-measured values showed that the BSAF method over-predicted tissue concentrations in M. arenaria by up to 2 orders of magnitude. The polyethylene-deduced CW method resulted in average ratios closer to 1 (0.43 ± 0.26, 3.7 ± 2.5, and 1.1 ± 1.2 for phenanthrene, pyrene, and chrysene, respectively, N = 26, uncertainty = ± 1σ)., (© 2015 SETAC.)

Polyethylene films were separated and recovered from polyethylene-aluminum composites derived from recycling multilayer postconsumer aseptic packaging. A brief study about the separation process by dissolving PE-aluminum (PE-Al) composites into a series of organic solvents with a combination of time and temperature is presented. Through this procedure, 56% polyethylene is recovered from this kind of composites in optimized conditions. DSC and TGA studies were performed to determine the thermal stability of recovered polyethylene films and to establish a comparison with a PE reference commercial product, demonstrating that recovered polyethylene films kept their thermal properties., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

A challenge in environmental passive sampling is determining when equilibrium is achieved between the sampler, target contaminants, and environmental phases. A common approach is the use of performance reference compounds (PRCs) to estimate target contaminant sampling rates and indicate degree of sampler equilibrium. One logistical issue associated with using PRCs is their sometimes exorbitant cost. To address PRC expense, this investigation 1) compared the performance of inexpensive PRCs (deuterated PAHs) and expensive PRCs ((13) C-labeled PCBs) to estimate dissolved PCB concentrations in freshwater and marine deployments, and 2) evaluated the use of smaller quantities of PRC relative to regular amounts used for estimating dissolved PAH and PCB concentrations. Saltwater and freshwater site average differences between total dissolved PCB concentrations calculated using the 2 classes of PRCs was 34 pg/L (20%) and 340 pg/L (51%), respectively, and in some deployments, statistical differences in PCB concentrations generated by the 2 types of PRCs were detected. However, no statistical differences were detected between total dissolved PAH and PCB for the 3 quantities of PRCs. In both investigations, individual dissolved PCB congeners and PAH compounds demonstrated comparable behavior as those expressed as total PCB or PAH dissolved concentrations. This research provides evidence that in some applications passive sampling using inexpensive and smaller quantities of PRCs can yield cost savings of approximately 75%. This approach appears most promising in the marine water column and when focusing on dissolved concentrations of low and medium molecular weight congeners or total PCBs., (Published 2014 SETAC. This article is a US Government work and, as such, is in the public domain in the USA.)

Three types of commercially available ultra-high molecular weight polyethylene (UHMWPE) acetabular cups currently used in total hip arthroplasty have been studied by means of Raman micro-spectroscopy to unfold the microstructural modification induced by the oxidative degradation after accelerated aging with and without lipid absorption. The three investigated materials were produced by three different manufacturing procedures, as follows: irradiation followed by remelting, one-step irradiation followed by annealing, 3-step irradiation and annealing. Clear microstructural differences were observed in terms of phase contents (i.e. amorphous, crystalline and intermediate phase fraction). The three-step annealed material showed the highest crystallinity fraction in the bulk, while the remelted polyethylene is clearly characterized by the lowest content of crystalline phase and the highest content of amorphous phase. After accelerated aging either with or without lipids, the amount of amorphous phase decreased in all the samples as a consequence of the oxidation-induced recrystallization. The most remarkable variations of phase contents were detected in the remelted and in the single-step annealed materials. The presence of lipids triggered oxidative degradation especially in the remelted polyethylene. Such experimental evidence might be explained by the highest amount of amorphous phase in which lipids can be absorbed prior to accelerated aging. The results of these spectroscopic characterizations help to rationalize the complex effect of different irradiation and post-irradiation treatments on the UHMWPE microstructure and gives useful information on how significantly any single step of the manufacturing procedures might affect the oxidative degradation of the polymer., (© The Author(s) 2014 Reprints and permissions: sagepub.co.uk/journalsPermissions.nav.)

The biogenic fraction of a simple solid recovered fuel (SRF) mixture (80 wt% printer paper/20 wt% high density polyethylene) is analyzed with the in-house developed adapted balance method (aBM). This fairly new approach is a combination of combustion elemental analysis (CHNS) and a data reconciliation algorithm based on successive linearisation for evaluation of the analysis results. This method shows a great potential as an alternative way to determine the biomass content in SRF. However, the employed analytical technique (CHNS elemental analysis) restricts the probed sample mass to low amounts in the range of a few hundred milligrams. This requires sample comminution to small grain sizes (<200 μm) to generate representative SRF specimen. This is not easily accomplished for certain material mixtures (e.g. SRF with rubber content) by conventional means of sample size reduction. This paper presents a proof of principle investigation of the sample preparation and analysis of an SRF model mixture with the use of cryogenic impact milling (final sample comminution) and the adapted balance method (determination of biomass content). The so derived sample preparation methodology (cutting mills and cryogenic impact milling) shows a better performance in accuracy and precision for the determination of the biomass content than one solely based on cutting mills. The results for the determination of the biogenic fraction are within 1-5% of the data obtained by the reference methods, selective dissolution method (SDM) and (14)C-method ((14)C-M)., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

The introduction of numerous formulations of Ultra-high molecular weight polyethylene (UHMWPE), which is widely used as a bearing material in orthopedic implants, necessitated screening of bearing couples to identify promising iterations for expensive joint simulations. Pin-on-disk (POD) testers capable of multidirectional sliding can correctly rank formulations of UHMWPE with respect to their predictive in vivo wear behavior. However, there are still uncertainties regarding POD test parameters for facilitating clinically relevant wear mechanisms of UHMWPE. Studies on the development of POD testing were briefly summarized. We systematically reviewed wear rate data of UHMWPE generated by POD testers. To determine if POD testing was capable of correctly ranking bearings and if test parameters outlined in ASTM F732 enabled differentiation between wear behavior of various formulations, mean wear rates of non-irradiated, conventional (25-50kGy) and highly crosslinked (≥90kGy) UHMWPE were grouped and compared. The mean wear rates of non-irradiated, conventional and highly crosslinked UHMWPEs were 7.03, 5.39 and 0.67mm(3)/MC. Based on studies that complied with the guidelines of ASTM F732, the mean wear rates of non-irradiated, conventional and highly crosslinked UHMWPEs were 0.32, 0.21 and 0.04mm(3)/km, respectively. In both sets of results, the mean wear rate of highly crosslinked UHMPWE was smaller than both conventional and non-irradiated UHMWPEs (p<0.05). Thus, POD testers can compare highly crosslinked and conventional UHMWPEs despite different test parameters. Narrowing the allowable range for standardized test parameters could improve sensitivity of multi-axial testers in correctly ranking materials., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Background: The purpose of this study was to evaluate wear debris in periprosthetic tissues at the time of revision total elbow arthroplasty. Polyethylene, metallic, and bone cement debris were characterized, and the tissue response was quantified., Materials and Methods: Capsular and medullary tissue samples were collected during revision surgery. Polyethylene debris was characterized by scanning electron microscopy after tissue digestion. The concentrations of metal and cement debris were quantified by inductively coupled plasma mass spectrometry. Tissue response was graded with a semiquantitative histologic method., Results: Polyethylene particle size varied from the submicron range to over 100 μm. The mean diameter ranged from 0.6 μm to about 1 μm. Particles in the synovial tissues were larger and less abundant than those in tissues from the medullary canal. Cement, titanium alloy, and low levels of cobalt-chrome debris were also present, with cement predominating over metal debris. Histiocyte response was associated with small polyethylene particles (0.5-2 μm), and giant cells were associated with large polyethylene particles (>2 μm). Histiocyte scores positively correlated with the polyethylene particle number and the presence of metal., Discussion: We have shown that periprosthetic tissues of total elbow patients who have undergone revision for loosening and osteolysis contain polyethylene, cement, and metal debris. Although the polyethylene particles were of a size and shape that have been previously shown to result in activation of phagocytic cells, osteolysis after total elbow arthroplasty is a multimodal process. Because of the presence of multiple wear particle sources, a cause-and-effect relationship between polyethylene debris and osteolysis cannot be established with certainty., (Copyright © 2013 Journal of Shoulder and Elbow Surgery Board of Trustees. Published by Mosby, Inc. All rights reserved.)

Gas chromatography/mass spectrometry (GC/MS) and matrix-assisted laser desorption/ionization time-of-flight (MALDI-ToF) mass spectrometry, in conjunction with various derivatization approaches, have been applied to structure determination of individual oligomers and molecular-mass distributions (MMD) in low-molecular mass polyethylene having an iodine terminus. Direct GC/MS analysis has shown that the samples under investigation composed of polyethyelene-iodides (major components) and n-alkanes. Exchange reaction with methanol in the presence of NaOH gave rise to methoxy-derivatives and n-alkenes. Electron ionization mass spectra have shown that the former contained terminal methoxy groups indicating the terminal position of the iodine atom in the initial oligomers. MMD parameters have been determined with the aid of MALDI mass spectrometry followed by preliminary derivatization-formation of covalently bonded charge through the reaction of iodides with triphenylphosphine, trialkylamines, pyridine or quinoline. The mass spectra revealed well-resolved peaks for cationic parts of derivatized oligomers allowing the determination of MMD. The latter values have been compared with those calculated from GC/MS data.

For centuries silver and silver compounds have been in use to control infection and avoid septicaemia in the care of burns and chronic wounds. Renewed interest has resulted in a number of Ag based dressings that are now widely used in burns centres. Despite extensive use, a systematic study of the chemical composition, release kinetics and biochemical action of these products has yet to be published. In this work we have characterized the morphology of four commercial Ag dressings by scanning electron microscopy and the silver content was determined to range between 1.39 mg/cm(2) and 0.03 mg/cm(2). Release kinetics in three different matrices (ultra pure water, normal saline solution and a human serum substitute) were determined. The highest rates were found in serum substitute, with a maximum of 4099 μg/(hcm(2)) to a minimum of 0.0001 μg/(hcm(2)). Our results show that the mean inhibitory concentrations are exceeded for most common pathogens in serum substitute and sterile water, but the presence of high Cl(-) concentrations tend to inactivate the dressings., (Copyright © 2012 Elsevier Ltd and ISBI. All rights reserved.)

Calf serum lubricants consisting of various polypeptide constituent fractions are routinely used in knee wear simulators as part of the standardized test protocol. Three calf sera (bovine, new-born and alpha) were diluted as per the recommendation of ISO 14243-3 and used in displacement-controlled knee wear simulators to investigate their effects on polyethylene wear. Biochemical analyses included measuring total polypeptide degradation, electrophoretic profiles and low-molecular weight polypeptide concentrations to elucidate their involvement in the wear process. The effects of the various calf sera constituent fractions on microbial growth were also explored. The polyethylene wear rates and the results from the biochemical analyses for the three calf serum lubricants were all found to be statistically significantly different from each other. The lubricant derived from the alpha-calf serum was closest in constituent fractions to human synovial fluid. It also showed the lowest polyethylene wear rate (14.38 +/- 0.85 mm3/million cycles) and the lowest amount of polypeptide degradation (7.77 +/- 3.87%). Furthermore, the alpha-calf serum lubricant was associated with the least amount of change in the electrophoretic profile, the least change in low-molecular weight polypeptide concentration, and the lowest microbial growth in the presence of sodium azide (a microbial inhibitor conventionally used in implant wear testing). Replacing sodium azide with a broad spectrum antibiotic-antimycotic eradicated the microbial growth. Some speculation was entertained regarding the effect of alpha-calf serum on colloid-mediated boundary lubrication. Based on the results, it was recommended that ISO 14243-3 be modified to include guidelines on calf serum constituent fractions that would favour using alpha-calf serum in order to improve the fidelity of the simulation in knee implant wear testing.

New colorimetric methods are described for determination of sub-milligram amounts of ultra-high molecular weight polyethylene (UHMWPE) wear particles. These methods are based on the irreversible binding of the fluorescein-conjugated bovine serum albumin or the hydrophobic dye Oil Red O to wear particles. UHMWPE particles bind both substances from their solutions and thus decrease the absorbance of these solutions. The decrease is linearly dependent on the amount of added wear particles in the sub-milligram range suitable for practical use. The newly developed method offers improved accuracy and precision compared to Fourier transformed infrared spectroscopy (Slouf M, et al. Quantification of UHMWPE wear in periprosthetic tissues of hip arthoplasty: description of a new method based on IR and comparison with radiographic appearance. Wear 2008;265:674-684.)., (Copyright © 2012 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.)

POSH are polyolefin oligomeric saturated hydrocarbons, such as oligomers from polyethylene or polypropylene. POSH that have migrated into foods are easily mistaken for mineral oil-saturated hydrocarbons (MOSH). In fact, both POSH and MOSH largely consist of highly isomerised branched and possibly cyclic hydrocarbons, both forming humps of unresolved components in gas chromatography. Chromatograms are reported to show typical elution patterns of POSH and help analysts distinguishing POSH from MOSH as far as possible. Since the structures of the POSH are not fundamentally different from those of the MOSH, it would be prudent to apply the evaluation of the MOSH. However, the migration is frequently beyond that for which safety has been demonstrated. This is shown for a few examples, particularly for powdered formula for babies.

A six-station displacement-controlled knee simulator with separately controlled left (L) and right (R) banks (three wear implants per bank) was commissioned for a total of three million cycles (Mc) following ISO 14243-3. A commissioning protocol was applied to compare the polyethylene wear among the six wear stations by exchanging the implants between wear stations. Changes in lubricant characteristics during wear testing, such as polypeptide degradation, low-molecular-weight polypeptide concentration, and possible microbial contamination were also assessed. The total mean wear rate for the implants was 23.60 +/- 1.96 mm3/Mc and this was of a similar magnitude to the mean wear rate for the same implant tested under similar conditions by DePuy Orthopaedics Inc. (Warsaw, IN). Repeated run-in wear was observed when the implants were exchanged between wear stations, suggesting that implants should be subjected to the same wear station throughout the duration of a wear test. The total polypeptide degradation for the implants measured 30.53 +/- 3.96 percent; the low-molecular-weight polypeptide concentration of the "used" lubricant for implants (0.131 +/- 0.012 g/L) was 3.3 times greater than the mean polypeptide concentration of the fresh, "unused" lubricant (0.039 +/- 0.004 g/L). This increase in low-molecular weight polypeptide concentration was suggested to be attributable to protein shear in the articulation of the implant, the circulation of the lubricant, and some proteolytic activity. Sodium azide was ineffective in maintaining a sterile environment for wear testing as a single, highly motile Gram-negative micro-organism was identified in the lubricant from wear tests.

A size-exclusion chromatography-Fourier transform infrared spectroscopy (SEC-FTIR) method for the analysis of high-density polyethylene copolymers was developed, providing superior resolution for the determination of short-chain branching as a function of time and improved repeatability by hardware adaptation and processing optimization. SEC-FTIR for characterization of polyolefins is a compromising technique. Best resolution in terms of molecular weight and molecular weight distribution requires a very low sample solution concentration in size-exclusion chromatography while best results from online infrared (IR) spectroscopy require as high concentrations as possible. The signal-to-noise ratio at the IR detector could be increased significantly after application of a bandpass filter instead of a steel mesh attenuator and furthermore influences of system instabilities could be decreased by changes in data processing. Reliable short-chain branching information in the high molecular weight section in respect to accuracy and repeatability with better chromatographic resolution could be achieved.

A new kind of wood plastic composite (WPC) was produced by compounding nonmetals from waste printed circuit boards (PCBs), recycled high-density polyethylene (HDPE), wood flour and other additives. The blended granules were then extruded to profile WPC products by a conical counter-rotating twin-screw extruder. The results showed that the addition of nonmetals in WPC improved the flexural strength and tensile strength and reduced screw withdrawal strength. When the added content of nonmetals was 40%, the flexural strength of WPC was 23.4 MPa, tensile strength was 9.6 MPa, impact strength was 3.03 J/m(2) and screw withdrawal strength was 1755 N. Dimensional stability and fourier transform infrared spectroscopy (FTIR) of WPC panels were also investigated. Furthermore, thermogravimetric analysis showed that thermal degradation of WPC mainly included two steps. The first step was the decomposition of wood flour and nonmetals from 260 to 380 degrees C, and the second step was the decomposition of HDPE from 440 to 500 degrees C. The performance and thermal behavior of WPC produced by nonmetals from PCBs achieves the standard of WPC. It offers a novel method to treat nonmetals from PCBs., (2010 Elsevier B.V. All rights reserved.)

Introduction: Information on the distribution of UHMWPE wear particles around joint replacements is essential for the understanding of aseptic loosening of implants., Material and Methods: Samples of soft tissue from around total hip arthroplasty (THA), which had a typical appearance of polyethylene granuloma, were collected from the places corresponding to the radiological zones of Gruen and DeLee. The samples were taken from 45 patients (group N1). Since the samples varied in macroscopic appearance and/or the technique of processing, a sub-group of 15 more uniform samples (group N2) were collected by the first author in order to ensure the maxi- mum reliability. The samples were examined for the extent of tissue damage and the amount of particles in each zone. The comprehensive orthopaedic evaluation of tissue damage was carried out as follows: the first author studied the joint replacement revision protocol and pre-operative radiograph in each patient. He evaluated the degree of damage in each zone and wrote down the results in the form of an ordered series according to increasing damage (relational statement). This ordered series was called orthopaedist's statement (OS). The amount of particles in each zone around THA was assessed by the IRc method developed in the laboratory of the second author. IRc method yielded numbers that were proportional to the volume of biologically active particles with size 0.1-10 microm in given zones. The set of numbers from IRc method for each individual case of THA was ordered in a series (relational statement). This ordered series was called a measurement statement (MS) and could be directly compared with orthopaedist's statement (OS). The OS's and MS's for each patient were statistically evaluated, independently for each group (N1=45, N2=15), and two hypotheses were tested: a) distribution of particles in various zones around THA is uniform, b) there is an agreement between OS and MS., Results: The number of UHMWPE wear particles in different periprosthetic zones within each patient was significantly different in both groups (N1 and N2) at the significance level of P=0.001. The OS's and MS's were identical at the significance level P=0.05. Moreover, maximum amount of particles was found in zones III and 7 in 40 patients out of 45., Discussion: Polyethylene wear debris is considered one of the major causes of THR failures. However, neither national nor international literature has provided a study that would show a statistically significant relationship between the numbers of wear particles in individual zones and the extent of tissue damage in these zones. This is most probably due to the fact that four independent methods had to be developed in order to compare OS's and MS's: 1) accurate technique of tissue sampling during THA revisions, 2) accurate method of isolating wear particles from the tissues collected, 3) efficient, reliable and reproducible quantification of UHMWPE particles and 4) correct method of statistical analysis for comparison of the orthopaedist's statements and the measurement statements for all patients involved., Conclusion: The distribution of wear particles in the periprosthetic tissues of THA is not uniform, i.e. the amount of wear particles of each patient varies from zone to zone. The extent of tissue damage in each zone, as assessed by the orthopaedic surgeon (OS), was in a good agreement with the volume of 0.1-10 microm particles obtained by IRc measurement (MS) of the zone. We have provided conclusive evidence that the highest number of particles is accumulated in zone III and zone 7. As the number of particles the zones varies and the greatest damage is repeatedly found in areas with the highest particle numbers, it can be concluded with certainly that wear particles are one of the main causes of aseptic joint implant failure.

This paper briefly reviews the latest progress in the analyses of the technologies for artificial hip joints; and in the researches directed to the features of UHMWPE debris obtained from all kinds of experimental conditions, to the wear process and wear mechanism, and to the factors which influence the wear mechanism. Furthermore, the signification of debris atlas was illustrated. Finally, future directions to be furthered were considered and envisaged. It is suggested that emphases be laid on the relationship between the UHMWPE debris feature and the wear mechanism, and be laid synergistic effects of biochemical environment and loading environment so as to establish the predictive wear models of artificial hip joints.

In this study di- and triblock copolymers of ethylene oxide (EO) and propylene oxide (PO) are analyzed by using CAP for one block and adsorption for the other block. This gives a complete picture of EO- and PO-based block copolymer with respect to the oligomers of both blocks. A full resolution of the individual oligomers can be achieved for both blocks up to an average molecular weight of 1000-1500 of each block.

Wear debris has been observed in shoulder arthroplasties that use an ultrahigh-molecular weight polyethylene (UHMWPE) glenoid component, and the biologic response to this debris contributes to aseptic loosening of the implant. The objective of this study was to assess the wear and particle morphology of a cross-linked UHMWPE prosthetic glenoid. To our knowledge, this is the first time a simulator with kinematic considerations for assessing wear has been used in a shoulder model. Shoulder wear testing was conducted on 2 groups of glenoids (n = 3 in each group) by use of an orthopaedic joint simulator to create worst-case scenario motions. One group was manufactured from conventional UHMWPE. The second was manufactured from 50-kGy cross-linked UHMWPE. The resulting wear rates for the conventional and cross-linked glenoid components were 46.7 +/- 2.6 mg/million cycles and 7.0 +/- 0.4 mg/million cycles, respectively. Particles isolated from the 2 groups showed similar morphologies; however, the calculated osteolytic potential of the cross-linked glenoid was significantly lower. The results of this study support the use of cross-linked UHMWPE glenoids in clinical applications.

We report on a novel lithography-free method for obtaining chemical submicron patterns of macromolecules on flat substrates. The approach is an advancement of the well-known microcontact printing scheme: While for classical microcontact printing lithographically produced masters are needed, we show that controlled wrinkling can serve as an alternative pathway to producing such masters. These can even show submicron periodicities. We expect upscaling to larger areas to be considerably simpler than that for existing techniques, as wrinkling results in a macroscopic deformation process that is not limited in terms of substrate size. Using this approach, we demonstrate successful printing of aqueous solutions of polyelectrolytes and proteins. We study the effectiveness of the stamping process and its limits in terms of periodicities and heights of the stamps' topographical features. We find that critical wavelengths are well below 355 nm and critical amplitudes are below 40 nm and clarify the failure mechanism in this regime. This will permit further optimization of the approach in the future.

Nanometre-sized particles of ultra-high molecular weight polyethylene have been identified in the lubricants retrieved from hip simulators. Tissue samples were taken from seven failed Charnley total hip replacements, digested using strong alkali and analysed using high-resolution field emission gun-scanning electron microscopy to determine whether nanometre-sized particles of polyethylene debris were generated in vivo. A randomised method of analysis was used to quantify and characterise all the polyethylene particles isolated. We isolated nanometre-sized particles from the retrieved tissue samples. The smallest identified was 30 nm and the majority were in the 0.1 microm to 0.99 microm size range. Particles in the 1.0 microm to 9.99 microm size range represented the highest proportion of the wear volume of the tissue samples, with 35% to 98% of the total wear volume comprised of particles of this size. The number of nanometre-sized particles isolated from the tissues accounted for only a small proportion of the total wear volume. Further work is required to assess the biological response to nanometre-sized polyethylene particles.

The aim of this work was to test and to compare different methods reported in the literature to quantify amine and aldehyde functions on the surface of polyethylene (PE) films treated by ammonia plasma and to specify their stability against time. A low pressure ammonia plasma reactor was used to functionalize PE films with amine groups, which could be subsequently used for further immobilization of biomolecules. In order to determine the density of amine groups on the surface of treated films, various molecule probes and spectrophotometric analytical methods have been investigated. Two methods using (i) sulfosuccinimidyl 6-[3'-(2-pyridyldithio)-propionamido] hexanoate (sulfo-LC-SPDP) and (ii) 2-iminothiolane (ITL) associated with bicinchoninic acid (BCA) have been proved to be reliable and sensitive enough to estimate the surface concentration of primary amine functions. The amount of primary amino groups on the functionalized polyethylene films was found to be between 1.2 and 1.4 molecules/nm2. In a second step, the surface concentration of glutaraldehyde (GA), which is currently used as a spacer arm before immobilization of biomolecules, has been assessed: two methods were used to determine the surface density of available aldehyde functions, after the reaction of GA with the aminated polyethylene film. The concentration of GA was found to be in the same range as primary amine concentration. The influence of aging time on the density of available amino and aldehyde groups on the surfaces were evaluated under different storage conditions. The results showed that 50% of the initial density of primary amine functions remained available after storage during 6 days of the PE samples in PBS (pH 7.6) at 4 degrees C. In the case of aldehyde groups, the same percentage of the initial density (50%) remained active after storage in air at RT over a longer period, i.e., 15 days.

The separation process in reversed-phase high-performance liquid chromatography employing C18 phases is mainly due to hydrophobic interactions. The separation of tocopherol isomers, exhibited by the C30 phases, however, is additionally driven by shape selectivity. This phenomenon is investigated by suspended-state nuclear magnetic resonance spectroscopy using the saturation transfer difference technique, which was originally introduced to study protein-ligand interactions. The interaction strength between beta-/gamma-tocopherol and three different stationary phases was estimated qualitatively. The nuclear magnetic resonance data are compared to chromatographic data, and a similar mode of interaction between the analytes and the stationary phases is elucidated.

A technically simple and inexpensive discontinuous turbidity assay for qualitative and/or quantitative assessments of polygalacturonic acid depolymerase activity is presented. The enzyme reaction is initiated by the addition of enzyme preparation to a reaction mixture containing 0.02% polygalacturonic acid (PGA) in acetate buffer. The progress of the reaction is monitored by terminating aliquots of the reaction mixture (via heat treatment at appropriate times), subsequently adding poly(diallyldimethylammonium chloride) (PDADMAC) for turbidity development (approximately 30 min), and then measuring the turbidity (typically at 420 nm) of the resulting PGA-PDADMAC complex-containing solution. PGA depolymerase activity causes a decrease in the observed turbidity of PGA-PDADMAC-containing solutions because the stability of the interpolyelectrolyte PGA-PDADMAC complex is a function of the degree of polymerization of the PGA. The rate of turbidity change is herein shown to be proportional to a relatively wide range of enzyme concentrations. The assay is demonstrated using a commercial pectinase preparation and tomato fruit extracts.