A Comparative Study on the Combustion Chemistry of Two Bio-hybrid Fuels: 1,3-Dioxane and 1,3-Dioxolane.

Bio-hybrid fuels are a promising solution to accomplish a carbon-neutral and low-emission future for the transportation sector. Two potential candidates are the heterocyclic acetals 1,3-dioxane (C4H8O2) and 1,3-dioxolane (C3H6O2), which can be produced from the combination of biobased feedstocks, carbon dioxide, and renewable electricity. In this work, comprehensive experimental and numerical investigations of 1,3-dioxane and 1,3-dioxolane were performed to support their application in internal combustion engines. Ignition delay times and laminar flame speeds were measured to reveal the combustion chemistry on the macroscale, while speciation measurements in a jet-stirred reactor and ethylene-based counterflow diffusion flames provided insights into combustion chemistry and pollutant formation on the microscale. Comparing the experimental and numerical data using either available or proposed kinetic models revealed that the combustion chemistry and pollutant formation differ substantially between 1,3-dioxane and 1,3-dioxolane, although their molecular structures are similar. For example, 1,3-dioxane showed higher reactivity in the low-temperature regime (500-800 K), while 1,3-dioxolane addition to ethylene increased polycyclic aromatic hydrocarbons and soot formation in high-temperature (>800 K) counterflow diffusion flames. Reaction pathway analyses were performed to examine and explain the differences between these two bio-hybrid fuels, which originate from the chemical bond dissociation energies in their molecular structures.

Effectiveness of tetrahydrofuran at enhancing the 1,4-dioxane degradation ability of activated sludge lacking prior exposure to 1,4-dioxane.

1,4-dioxane (DX) is a contaminant of emerging concern in water environments. The enrichment of DX-degrading bacteria indigenous to activated sludge is key for the efficient biological removal of DX in wastewater. To identify an effective substrate, which enables the selective enrichment of DX-degrading bacteria and has lower toxicity and persistence than DX, this study explored the effectiveness of tetrahydrofuran (THF) at enhancing the DX degradation ability of activated sludge without historical exposure to DX. Although the activated sludge initially exhibited negligible ability to degrade DX (100 mg-C/L) as the sole carbon source, the repeated batch cultivation on THF could enrich bacterial populations capable of degrading DX, inducing the DX degradation ability in activated sludge as effectively as DX did. The THF-enrichment culture after 4 weeks degraded 100 mg-C/L DX almost completely within 21 d. Sequencing analyses revealed that soluble di-iron monooxygenase group 5C, including THF/DX monooxygenase, would play a dominant role in the initial oxidation of DX in THF-enrichment culture, which completely differed from the enrichment culture cultivated on DX. The results indicate that THF can be applied as an effective substrate to enhance the DX degradation ability of microbial consortia, irrespective of the intrinsic ability.

Remedial strategies for abating 1,4-dioxane pollution-special emphasis on diverse biotechnological interventions.

1,4-dioxane is a heterocyclic ether used as a polar industrial solvent and are released as waste discharges. 1,4-dioxane deteriorates health and quality, thereby attracts concern by the environment technologists. The need of attaining sustainable development goals have resulted in search of an eco-friendly and technically viable treatment strategy. This extensive review is aimed to emphasis on the (a) characteristics of 1,4-dioxane and their occurrence in the environment as well as their toxicity, (b) remedial strategies, such as physico-chemical treatment and advanced oxidation techniques. Special reference to bioremediation that involves diverse microbial strains and their mechanism are highlighted in this review. The role of macronutrients, stimulants and other abiotic cofactors in the biodegradation of 1,4-dioxane is discussed lucidly. We have critically discussed the inducible enzymes, enzyme-based remediation, distinct instrumental method of analyses to know the fate of intermediates produced from 1,4-dioxane biotransformation. This comprehensive survey also tries to put forth the different toxicity assessment tools used in evaluating the extent of detoxification of 1,4-dioxane achieved through biotransforming mechanism. Conclusively, the challenges, opportunities, techno-economic feasibility and future prospects of implementing 1,4-dioxane through biotechnological interventions are also discussed.

Assessment of Non-Occupational 1,4-Dioxane Exposure Pathways from Drinking Water and Product Use.

1,4-Dioxane is a persistent and mobile organic chemical that has been found by the United States Environmental Protection Agency (USEPA) to be an unreasonable risk to human health in some occupational contexts. 1,4-Dioxane is released into the environment as industrial waste and occurs in some personal-care products as an unintended byproduct. However, limited exposure assessments have been conducted outside of an occupational context. In this study, the USEPA simulation modeling tool, Stochastic Human Exposure and Dose Simulator-High Throughput (SHEDS-HT), was adapted to estimate the exposure and chemical mass released down the drain (DTD) from drinking water consumption and product use. 1,4-Dioxane concentrations measured in drinking water and consumer products were used by SHEDS-HT to evaluate and compare the contributions of these sources to exposure and mass released DTD. Modeling results showed that compared to people whose daily per capita exposure came from only products (2.29 × 10-7 to 2.92 × 10-7 mg/kg/day), people exposed to both contaminated water and product use had higher per capita median exposures (1.90 × 10-6 to 4.27 × 10-6 mg/kg/day), with exposure mass primarily attributable to water consumption (75-91%). Last, we demonstrate through simulation that while a potential regulatory action could broadly reduce DTD release, the proportional reduction in exposure would be most significant for people with no or low water contamination.

Evaluation of 1,4-dioxane attenuation processes at the Gelman Site, Michigan, USA.

1,4-Dioxane released at the Gelman Site in Washtenaw County, Michigan, produced a series of contaminant plumes migrating up to 3 km through a heterogenous glacial aquifer system. An analysis of 1,4-dioxane concentrations in the Eastern Area of the Gelman Site between 2011 and 2017 documented a mass balance deficit of 2200 kg in excess of 2100 kg of 1,4-dioxane removed via remediation. Five mechanisms were evaluated to account for the mass deficiency: sorption, matrix diffusion, biodegradation, surface discharge, and bypass of the existing monitoring well network. The mass of 1,4-dioxane sorbed to aquifer and aquitard materials and the mass of 1,4-dioxane diffused into low permeability zones were estimated. However, decreasing aqueous concentrations across most of the contaminated area between 2011 and 2017 are expected to induce desorption and back diffusion during this period. Surface water discharge to a storm drain in the downgradient portion of the site was analyzed using concentration measurements and stream gage data. Results suggest that 1,4-dioxane mass entering the drain during the period between 2011 and 2017 was insufficient to account for the mass deficiency. Although available geochemical measurements indicate predominantly anaerobic aquifer conditions at the Gelman Site, biodegradation of 1,4-dioxane was estimated using first order decay rate constants from other sites where conditions may be more favorable. Results suggest that biodegradation could explain some but not all of the missing mass. Bypass of the downgradient monitoring well network is the most parsimonious explanation for the 1,4-dioxane mass deficit. This conclusion is supported by documented flow path complexity through the aquifer system and the sparse density of monitoring wells in the downgradient Eastern Area. These findings underscore the importance of characterizing aquifer heterogeneity when modeling and remediating persistent groundwater contaminants such as 1,4-dioxane.

Be alert for vapor intrusion of 1,4-dioxane from contaminated groundwater.

Vapor intrusion (VI) poses significant environmental problems that can degrade indoor air and pose human health risks. This study focuses on 1,4-dioxane, a widely-used volatile organic compound (VOC) that is found in groundwater, however, this compound has not received much attention in indoor air and measurement methods are not well developed. 1,4-dioxane is sufficiently volatile and highly mobile in groundwater, and thus can present a VI risk. In this study, we develop a sensitive analytical method for quantifying airborne 1,4-dioxane, provide a performance evaluation of the method, and initiate preliminary field measurements above a 1,4-dioxane groundwater plume. The method uses passive sampling, automated thermal desorption, and gas chromatography/mass spectroscopy. Numerous other VOCs can be simultaneously measured. A low detection limit (0.067 µg/m3) is attained, which allows quantification at concentrations below health-based guidelines. The performance evaluation suggests limits to sampling times in high humidity environments and other means to ensure good performance. The scenario analyses demonstrate potential impacts from shallow plumes, especially in flooded basements, and thus monitoring of 1,4-dioxane vapor intrusion in the flood season is an urgent need.

Implementation of initial emission mitigation measures for 1,4-dioxane in Germany: Are they taking effect?

Since our comprehensive investigation of finished drinking water in Germany obtained from managed aquifer recharge systems in the period 2015-2016, which revealed widespread contamination with 1,4-dioxane, mitigation measures (integration of AOP units, shutdown or alteration of production processes) have been implemented at some sites. In this study, we conducted follow-up tests on surface water concentrations and associated finished drinking water concentrations in 2017/2018, to evaluate the effectiveness of these measures. Our findings demonstrate that the emission mitigation measures had considerably reducing effects on the average 1,4-dioxane drinking water concentrations for some of the previously severely affected areas (Lower Franconia: -54%, Passau: -88%). Conversely, at notoriously contaminated sites where neither monitoring nor mitigation measures were introduced, the drinking water concentrations stagnated or even increased. Drinking water concentrations determined via a modified US EPA method 522 ranged from below LOQ (0.034 µg/L) up to 1.68 µg/L in all drinking water samples investigated. In river water samples, the maximum concentration exceeded 10 µg/L. Effluents of wastewater treatments plants containing 1,4-dioxane (5 µg/L-1.75 mg/L) were also analyzed for other similar cyclic ethers by suspected target screening. Thus, 1,3-dioxolane and three other derivatives were tentatively identified in effluents from the polyester processing or manufacturing industry. 1,3-Dioxolane was present in concentrations >1.2 mg/L at one site, exceeding up to sevenfold the 1,4-dioxane concentration found there. At another site 2-methyl-1,3-dioxolane was still found 13 km downstream of the discharge point, indicating that ethers analogous to 1,4-dioxane should be further considered regarding their occurrence and fate in wastewater treatment and the aquatic environment.

Greenhouse gases emissions from duckweed pond system treating polyester resin wastewater containing 1,4-dioxane and heavy metals.

Phytoremediation of polyester resin wastewater containing 1,4-dioxane and heavy metals using Lemna gibba (L.gibba) was enhanced by incorporation of perforated polyethylene carrier materials (PCM) onto the duckweed pond (DWP) system. The DWP module was operated at a hydraulic retention times (HRTs) of 2, 4 and 6 days and as well as 1,4-dioxane loading rate of 16, 25 and 48 g/m3.d. The maximum removal efficiency of 54 ± 2.5% was achieved for 1,4-dioxane at an HRT of 6 days and loading rate of 16 g1,4-dioxane/m3.d. Similarly, the DWP system provided removal efficiencies of 28.3 ± 2.1, 93.2 ± 7.6, 95.7 ± 8.9 and 93.6 ± 4.9% for Cd2+, Cu2+, Zn2+ and Ni2+ at influent concentration of 0.037 ± 0.01, 1.2 ± 0.9, 27.2 ± 4.7 and 4.6 ± 1.2 mg/L respectively. The structural analysis by Fourier-transform infrared spectroscopy (FTIR) clearly displayed a reduction of 1,4- dioxane in the treated effluent. A strong peak was detected for L. gibba plants at frequency of 3417.71 cm-1 due to N-H stretching, which confirm the proposed mechanism of partially conversion of 1,4-dioxane into amino acids. Glycine, serine, aspartic, threonine and alanine content were increased in L. gibba by values of 35 ± 2.2, 40 ± 3.2, 48 ± 3.7, 31 ± 2.8, and 56 ± 4.1%, respectively. The contribution of DWP unit as a greenhouse gases (GHG) emissions were relatively low (1.65 gCO2/Kg BODremoved.d., and 18.3 gCO2/Kg biomass.d) due to photosynthesis process, low excess sludge production and consumption of CO2 for nitrification process (1.4 gCO2/kgN removed.d). Based on these results, it is recommended to apply such a technology for treatment of polyester resin wastewater containing 1,4-dioxane and heavy metals at a HRT not exceeding 6 days.

Kinetic characterization of purified laccase from Trametes hirsuta: a study on laccase catalyzed biotransformation of 1,4-dioxane.

OBJECTIVE: Laccase is one of the best known biocatalysts which degrade wide varieties of complex molecules that are both non-cyclic and cyclic in structure. The study focused on enzyme kinetics of a purified laccase from Trametes hirsuta L. fungus and its application on biotransformation of a carcinogenic molecule 1,4-dioxane. RESULTS: Laccase was purified from white-rot fungus T. hirsuta L. which showed specific activity of 978.34 U/mg after the purification fold of 54.08. The stable laccase activity (up to 16 h) is shown at 4-6 pH and 20-40 °C temperature range. The purified enzyme exhibited significant stability for 10 metal ions up to 10 mM concentration, except for Fe2+ and Hg2+. The Cu2+ ion induced laccase activity up to 142% higher than the control at 10 mM concentration. The laccase enzyme kinetic parameters Km was 20 ± 5 µM and 400 ± 60 µM, whereas Kcat was 198.29 ± 0.18/s and 80.20 ± 1.59/s for 2,2'-azino-bis (3-ethylbenzothiazoline-6-sulphonic acid) (ABTS) and guaiacol respectively. The cyclic ether 1,4-dioxane (100 ppm) was completely degraded in presence of purified laccase within 2 h of incubation and it was confirmed by HPLC and GC analysis. The oxidation reaction was accelerated by 25, 22, 6 and 19% in presence of 1 mM syringaldehyde, vanillin, ABTS and guaiacol mediators respectively. CONCLUSIONS: In this study, fungal laccase (a natural biocatalyst) based degradation of synthetic chemical 1,4-dioxane was reported for the first time. This method has added advantages over the multiple methods reported earlier being a natural remedy.

Solvent extraction and gas chromatography-mass spectrometric determination of probable carcinogen 1,4-dioxane in cosmetic products.

In the present work, a method based on solvent extraction and gas chromatography-mass spectrometry (GC-MS) has been validated for the determination of 1,4-dioxane in cosmetics. Various solvents including ethyl acetate, hexane, methanol, dichloromethane and acetone have been used for the extraction of 1,4-dioxane, among them the ethyl acetate was found to be the most efficient extracting solvent. This method has offered excellent quality parameters for instance linearity (R2 > 0.9991), limit of detection (LOD, 0.00065-0.00091 µg/mL), limit of quantification (LOQ, 0.00217-0.00304 µg/mL) and, precision intra-day (1.65-2.60%, n = 5) and inter-day (0.16-0.32%, n = 5) in terms of relative standard deviation (RSD%). A total of thirty-nine cosmetic samples of different brands and origin have been studied. Among them, the 1,4-dioxane was found in twenty-three samples (FB1-FB7, MC1-MC4, MC6-MC8, HS3, HS5, BL1-BL3, BL5 and PLD1-PLD3) at the levels between 0.15 µg/mL and 9.92 µg/mL, whereas in sixteen samples (MC5, HS1, HS2, SG1-SG5, BL4 and HP1- HP6) was found to be not detected. The recovery values were achieved between 93% and 99% in both low and high level of spiked samples. In comparison to the traditional analytical techniques, the proposed method was found to be very sensitive and cost-effective for the routine analysis of 1,4-dioxane at low concentration in cosmetics.

The determination of 1,4-dioxane in cosmetic products by gas chromatography with tandem mass spectrometry.

1,4-dioxane is a potential human carcinogen and contaminant produced during the manufacturing process from specific cosmetic ingredients, such as certain detergents and emulsifiers. As such, 1,4-dioxane is not identified on product ingredient labels. To assess the concentration of 1,4-dioxane in cosmetic products, a gas chromatography-tandem mass spectrometry (GC-MS/MS) method using pulsed split injection and electron ionization was developed and validated. For liquid cosmetic products such as shampoo and lotion, test portions were extracted using fast ultrasound-assisted extraction (UAE) procedure without sample cleanup. For solid products (e.g. beauty bars), a C18 solid phase extraction (SPE) procedure was optimized to reduce potential interferences. The corresponding stable isotopically labeled analogue (1,4-dioxane-d8) was selected as an internal standard to compensate for matrix effects and sample recovery. Method recovery experiments were performed in lotion, oil gel, hair detangler, bubble bath and beauty bar (solid) sample matrices with recoveries of 84-108% and relative standard deviations less than 5% at three spike concentrations. Method limits of detection (LOD) and quantification (LOQ) for 1,4-dioxane were determined at 0.2 µg/g and 0.5 µg/g, respectively. The method was successfully used to determine 1,4-dioxane in 82 leave-on and rinse-off cosmetic products marketed toward children including bath products, hair treatment, lotions, beauty bars, washes, shampoos, and other products. 1,4-dioxane was detected in 47 of the 82 products with an average concentration of 1.54 µg/g (range: 0.23-15.3 µg/g). The method can increase sample throughput and reduce matrix-induced interferences.

1,4-Dioxane cosolvency impacts on trichloroethene dissolution and sorption.

Solvent stabilizer 1,4-dioxane, an emerging recalcitrant groundwater contaminant, was commonly added to chlorinated solvents such as trichloroethene (TCE), and the impact of co-disposal on contaminant transport processes remains uncertain. A series of batch equilibrium experiments was conducted with variations of 1,4-dioxane and TCE composition to evaluate aqueous dissolution of the two components and their sorption to aquifer sediments. The solubility of TCE increased with increasing amounts of 1,4-dioxane, indicating that 1,4-dioxane acts as a cosolvent causing solubility enhancement of co-contaminants. The solubilization results compared favorably with predictions using the log-linear cosolvency model. Equilibrium sorption coefficients (Kd and Kf) were also measured for different 1,4-dioxane and TCE compositions, and the findings indicate that both contaminants adsorb to aquifer sediments and TCE Kd values increased with increasing organic matter content. However, the Kd for TCE decreased with increases in 1,4-dioxane concentration, which was attributed to cosolvency impacts on TCE solubility. These findings further advance our understanding of the mass-transfer processes controlling groundwater plumes containing 1,4-dioxane, and also have implications for the remediation of 1,4-dioxane contamination.

Abiotic and bioaugmented granular activated carbon for the treatment of 1,4-dioxane-contaminated water.

1,4-Dioxane is a probable human carcinogen and an emerging contaminant that has been detected in surface water and groundwater resources. Many conventional water treatment technologies are not effective for the removal of 1,4-dioxane due to its high water solubility and chemical stability. Biological degradation is a potentially low-cost, energy-efficient approach to treat 1,4-dioxane-contaminated waters. Two bacterial strains, Pseudonocardia dioxanivorans CB1190 (CB1190) and Mycobacterium austroafricanum JOB5 (JOB5), have been previously demonstrated to break down 1,4-dioxane through metabolic and co-metabolic pathways, respectively. However, both CB1190 and JOB5 have been primarily studied in laboratory planktonic cultures, while most environmental microbes grow in biofilms on surfaces. Another treatment technology, adsorption, has not historically been considered an effective means of removing 1,4-dioxane due to the contaminant's low Koc and Kow values. We report that the granular activated carbon (GAC), Norit 1240, is an adsorbent with high affinity for 1,4-dioxane as well as physical dimensions conducive to attached bacterial growth. In abiotic batch reactor studies, 1,4-dioxane adsorption was reversible to a large extent. By bioaugmenting GAC with 1,4-dioxane-degrading microbes, the adsorption reversibility was minimized while achieving greater 1,4-dioxane removal when compared with abiotic GAC (95-98% reduction of initial 1,4-dioxane as compared to an 85-89% reduction of initial 1,4-dioxane, respectively). Bacterial attachment and viability was visualized using fluorescence microscopy and confirmed by amplification of taxonomic genes by quantitative polymerase chain reaction (qPCR) and an ATP assay. Filtered samples of industrial wastewater and contaminated groundwater were also tested in the bioaugmented GAC reactors. Both CB1190 and JOB5 demonstrated 1,4-dioxane removal greater than that of the abiotic adsorbent controls. This study suggests that bioaugmented adsorbents could be an effective technology for 1,4-dioxane removal from contaminated water resources.

Spectroscopic methods for aqueous cyclodextrin inclusion complex binding measurement for 1,4-dioxane, chlorinated co-contaminants, and ozone.

Recalcitrant organic contaminants, such as 1,4-dioxane, typically require advanced oxidation process (AOP) oxidants, such as ozone (O3), for their complete mineralization during water treatment. Unfortunately, the use of AOPs can be limited by these oxidants' relatively high reactivities and short half-lives. These drawbacks can be minimized by partial encapsulation of the oxidants within a cyclodextrin cavity to form inclusion complexes. We determined the inclusion complexes of O3 and three common co-contaminants (trichloroethene, 1,1,1-trichloroethane, and 1,4-dioxane) as guest compounds within hydroxypropyl-ß-cyclodextrin. Both direct (ultraviolet or UV) and competitive (fluorescence changes with 6-p-toluidine-2-naphthalenesulfonic acid as the probe) methods were used, which gave comparable results for the inclusion constants of these species. Impacts of changing pH and NaCl concentrations were also assessed. Binding constants increased with pH and with ionic strength, which was attributed to variations in guest compound solubility. The results illustrate the versatility of cyclodextrins for inclusion complexation with various types of compounds, binding measurement methods are applicable to a wide range of applications, and have implications for both extraction of contaminants and delivery of reagents for treatment of contaminants in wastewater or contaminated groundwater.

Mechanism of 1,4-dioxane microbial degradation revealed by 16S rRNA and metatranscriptomic analyses.

1,4-Dioxane (dioxane), a probable human carcinogen, often exists in industrial wastewater and domestic sewage. In this study, we applied 16S rRNA and metatranscriptomic methods to analyze the dioxane biodegradation mechanism by activated sludge. Tetrahydrofuran (THF) was added as an essential co-metabolite to promote the degradation of dioxane. We found the dioxane removal ratio increased with increasing THF concentrations. When the THF concentration increased from 60.0 to 200.0 mg/L, the dioxane degradation rate was stable. Three additions of ∼60.0 mg/L THF resulted in better dioxane degradation than one addition of 200 mg/L THF. Ammonia-oxidizing and denitrifying bacteria with methane monooxygenases (MOs) and ammonia MOs played the most important roles during the degradation of dioxane. Kyoto Encyclopedia of Genes and Genomes metabolic pathway and functional genes analyses showed that the activated sludge system was complex and stable when dioxane was added. In future studies, primers should be designed to identify specific bacteria and functional MO genes, which would help reveal the function of various bacteria and their MOs during dioxane degradation.

1,4-Dioxane drinking water occurrence data from the third unregulated contaminant monitoring rule.

This study examined data collected from U.S. public drinking water supplies in support of the recently-completed third round of the Unregulated Contaminant Monitoring Rule (UCMR3) to better understand the nature and occurrence of 1,4-dioxane and the basis for establishing drinking water standards. The purpose was to evaluate whether the occurrence data for this emerging but federally-unregulated contaminant fit with common conceptual models, including its persistence and the importance of groundwater contamination for potential exposure. 1,4-Dioxane was detected in samples from 21% of 4864 PWSs, and was in exceedance of the health-based reference concentration (0.35µg/L) at 6.9% of these systems. In both measures, it ranked second among the 28 UCMR3 contaminants. Although much of the focus on 1,4-dioxane has been its role as a groundwater contaminant, the detection frequency for 1,4-dioxane in surface water was only marginally lower than in groundwater (by a factor of 1.25; p<0.0001). However, groundwater concentrations were higher than those in surface water (p<0.0001) and contributed to a higher frequency of exceeding the reference concentration (by a factor of 1.8, p<0.0001), indicating that surface water sources tend to be more dilute. Sampling from large systems increased the likelihood that 1,4-dioxane was detected by a factor of 2.18 times relative to small systems (p<0.0001). 1,4-Dioxane detections in drinking water were highly associated with detections of other chlorinated compounds particularly 1,1-dichlorethane (odds ratio=47; p<0.0001), which is associated with the release of 1,4-dioxane as a chlorinated solvent stabilizer. Based on aggregated nationwide data, 1,4-dioxane showed evidence of a decreasing trend in concentration and detection frequency over time. These data suggest that the loading to drinking water supplies may be decreasing. However, in the interim, some water supply systems may need to consider improving their treatment capabilities in response to further regulatory review of this compound.

Determining the Residual Characteristics of Alkylphenols, Arsenic, and Lead as well as Assessing the Exposures of 1,4-Dioxane from Household Food Detergents.

Food detergents are commonly used in households. The main components of detergents include surfactants and water. It has been found that certain compounds, which may cause health concerns, appear in food detergents, such as alkylphenols, arsenic, and lead. After applying food detergents is when people may be exposed to various levels of these chemicals when there are residues. In this study, the Taguchi experimental design was performed to determine the possible factors that might affect the residual characteristics of food detergent on dishware, fruits, and vegetables. The results showed that the variety of detergent was found to be the most significant factor affecting the residue amounts of arsenic (62.9%) and lead (71.6%) on fruits and vegetables, whereas the concentration of detergent used affected the amount of lead residue only (10.5%). On the other hand, dishware material, the concentration of analytes, immersion time, and type of surfactant contributed to arsenic residues on dishware, whereas technical nonylphenol isomer residues on dishware increased as the concentration of spiked analyte increased. In addition, the occurrence of 1,4-dioxane, a possible human carcinogen, in household food detergents in Taiwan was also determined in this research by solid-phase microextraction and GC-MS. Among the 80 detergent samples, 71 contained different concentrations ranges of 1,4-dioxane, from 0.03 to ~3.73 µg/g. In the exposure assessment, it was estimated that the maximum amounts of 1,4-dioxane in contact with the skin from the use of household food detergent in Taiwan was 0.015 µg/kg/day.

An Analytical Method for Determining Residual Lactide in Polylactide by Gas Chromatography.

An analytical method to determine the residual lactide in polylactide (PLA) was proposed using an internal standard method of gas chromatography (GC). PLA samples and diphenyl ether (DPE) as an internal standard were dissolved in dichloromethane, then PLA was precipitated in anhydrous alcohol. The residual lactide and DPE were extracted to alcohol for GC analysis. At room temperature, lactide could react with alcohol and change into ethyl lactoyl lactate (ELL), but the relative response factor of lactide versus DPE could be obtained through a numerical analysis method. Therefore, the residual lactide content could be quantitatively calculated in PLA. The relative standard deviation (RSD) of the measurements is not more than 7.0%, indicating that the method is suitably precise.

A new approach to improve the local compressive properties of PPDO self-expandable stent.

The radial performance of bioabsorbable polymeric intravascular stents is extremely important in assessing the efficiency of these devices in expanding narrow lumen, reducing stent recoil, and recovering to their original states after suffering from pulsating pressure. However, these stents remain inferior to metallic stents. Several thermal treatment conditions (60°C, 80°C, and 100°C for 1h) were investigated to improve the characteristics of poly(p-dioxanone) (PPDO) self-expandable stents. The local compressive force, stiffness, and viscoelasticity of these stents were also evaluated. Wide-angle X-ray diffraction and different scanning calorimetry measurements were performed to evaluate the recrystalline and thermodynamic changes of molecular chains. The declining conformer entropy of PPDO monofilaments was examined via energy analysis. The untreated stents had compressive modules of 514.80±70.59mN/mm, which was much higher than those of 80°C and 100°C treated stents (332.35±66.08mN/mm and 394.31±64.71mN/mm, respectively). Nevertheless, 100°C annealing stents had less stress relaxation and prior elastic recovery rate of 82.32±3.43mN and 92.55±1.61%, respectively, showing a much better shape stability than untreated stents (139.51±16.67mN and 86.18±3.57%, respectively). These findings present important clinical implications in the stent manufacturing process and warrant further study to develop new bioabsorbable stents with outstanding clinical efficacy.

Simultaneous determination of the potential carcinogen 1,4-dioxane and malodorous alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes in environmental waters by solid-phase extraction and gas chromatography tandem mass spectrometry.

1,4-dioxane is a synthetic industrial solvent used in various industrial processes, and it is a probable human carcinogen whose presence in the aquatic environment is frequently reported. Alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes are compounds that have been identified as causing several odor episodes in waters over the last years, with the result of downtime of drinking water treatment plants. According to published studies, some of these episodes may be caused either by resins synthesis processes, or by industrial residues added to dehydrated sludge in wastewater treatment plants (WWTPs) in order to increase biogas production efficiency. Analytical methods based on closed loop stripping analysis (CLSA) are routinely used when taste and odor events appear, but this technique has demonstrated to be unsuitable to determine 1,4-dioxane at trace levels. In this context, drinking water companies tend to focus on determining odorous compounds, but not on those compounds that are potentially harmful. The suitability of a SPE method and further analysis by GC/MS-MS to simultaneously determine 1,4-dioxane and alkyl-1,3-dioxanes and dioxolanes has been demonstrated. Recoveries in surface waters spiked at 25ng/L ranged from 76% to 105%, whereas method quantification limits (MQLs) varied from 0.7 to 26ng/L for dioxanes, and dioxolanes and 50ng/L for 1,4-dioxane. Uncertainties were evaluated at two different concentrations, 0.02µg/L and 0.4µg/L, with values of 25% for 1,4-dioxane, and of 16-28% for alkyl-1,3-dioxanes and alkyl-1,3-dioxolanes for the later. The methodology has been successfully applied to samples from the aquifer of the Llobregat River (NE. Spain).