Phase transitions of fluorotelomer alcohols at the water|alkane interface studied via molecular dynamics simulation.

Fluorosurfactants are long-lasting environmental pollutants that accumulate at interfaces ranging from aerosol droplet surfaces to cell membranes. Modeling of adsorption-based removal technologies for fluorosurfactants requires accurate simulation methods which can predict their adsorption isotherm and monolayer structure. Fluorotelomer alcohols with one or two methylene groups adjacent to the alcohol (7 : 1 FTOH and 6 : 2 FTOH, respectively) are investigated using the OPLS-AA force field at the water|hexane interface, varying the interfacial area per surfactant. The acquired interfacial pressure isotherms and monolayer phase behavior are compared with previous experimental results. The results are consistent with the experimental data inasmuch as, at realistic adsorption densities, only 7 : 1 FTOH shows a phase transition between liquid-expanded (LE) and 2D crystalline phases. Structures of the LE and crystalline phases are in good agreement with the sticky disc and Langmuir defective crystal models, respectively, used previously to interpret experimental data. Interfacial pressure of the LE phase agrees well with experiment, and sticky disc interaction parameters indicate no 2D LE-gas transition is present for either molecule. Conformation analysis reveals 7 : 1 FTOH favors conformers where the OH dipole is perpendicular to the molecular backbone, such that the crystalline phase is stabilized when these dipoles align.

Structure of the Hexadecane Rotator Phase: Combination of X-ray Spectra and Molecular Dynamics Simulation.

Rotator phases are rotationally disordered plastic crystals, some of which can form upon freezing of alkane at alkane-water interfaces. Existing X-ray diffraction studies show only partial unit cell information for rotator phases of some alkanes. This includes the rotator phase of n-hexadecane, which is a transient metastable phase in pure alkane systems, but shows remarkable stability at interfaces when mediated by a surfactant. Here, we combine synchrotron X-ray diffraction data and molecular dynamics (MD) simulations, reporting clear evidence of the face-centered orthorhombic RI rotator phase from spectra for two hexadecane emulsions, one stabilized by Brij C10 and another by Tween 40 surfactants. MD simulations of pure hexadecane use the recently developed Williams 7B force field, which is capable of reproducing crystal-to-rotator phase transitions, and it also predicts the crystal structure of the RI phase. Full unit cell information is obtained by combining unit cell dimensions from synchrotron data and molecular orientations from MD simulations. A unit cell model of the RI phase is produced in the crystallographic information file (CIF) format, with each molecule represented by a superposition of four rotational positions, each with 25% occupancy. Powder diffraction spectra computed using this model are in good agreement with the experimental spectra.

Extension of the TraPPE Force Field for Battery Electrolyte Solvents.

Optimizing electrolyte formulations is key to improving performance of Li-/Na-ion batteries, where transport properties (diffusion coefficient, viscosity) and permittivity need to be predicted as functions of temperature, salt concentration and solvent composition. More efficient and reliable simulation models are urgently needed, owing to the high cost of experimental methods and the lack of united-atom molecular dynamics force fields validated for electrolyte solvents. Here the computationally efficient TraPPE united-atom force field is extended to be compatible with carbonate solvents, optimizing the charges and dihedral potential. Computing the properties of electrolyte solvents, ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and dimethoxyethane (DME), we observe that the average absolute errors in the density, self-diffusion coefficient, permittivity, viscosity, and surface tension are approximately 15% of the corresponding experimental values. Results compare favorably to all-atom CHARMM and OPLS-AA force fields, offering computational performance improvement of at least 80%. We further use TraPPE to predict the structure and properties of LiPF6 salt in these solvents and their mixtures. EC and PC form complete solvation shells around Li+ ions, while the salt in DMC forms chain-like structures. In the poorest solvent, DME, LiPF6 forms globular clusters despite DME's higher permittivity than DMC.

There's something in the air: A review of sources, prevalence and behaviour of microplastics in the atmosphere.

Literature regarding microplastics in the atmosphere has advanced in recent years. However, studies have been undertaken in isolation with minimal collaboration and exploration of the relationships between air, deposition and dust. This review collates concentrations (particle count and mass-based), shape, size and polymetric characteristics for microplastics in ambient air (m3), deposition (m2/day), dust (microplastics/g) and snow (microplastics/L) from 124 peer-reviewed articles to provide a holistic overview and analysis of our current knowledge. In summary, ambient air featured concentrations between <1 to >1000 microplastics/m3 (outdoor) and <1 microplastic/m3 to 1583 ± 1181 (mean) microplastics/m3 (indoor), consisting of polyethylene terephthalate, polyethylene, polypropylene. No difference (p > 0.05) was observed between indoor and outdoor concentrations or the minimum size of microplastics (p > 0.5). Maximum microplastic sizes were larger indoors (p < 0.05). Deposition concentrations ranged between 0.5 and 1357 microplastics/m2/day (outdoor) and 475 to 19,600 microplastics/m2/day (indoor), including polyethylene, polystyrene, polypropylene, polyethylene terephthalate. Concentrations varied between indoor and outdoor deposition (p < 0.05), being more abundant indoors, potentially closer to sources/sinks. No difference was observed between the minimum or maximum reported microplastic sizes within indoor and outdoor deposition (p > 0.05). Road dust concentrations varied between 2 ± 2 and 477 microplastics/g (mean), consisting of polyvinyl chloride, polyethylene, polypropylene. Mean outdoor dust concentrations ranged from <1 microplastic/g (remote desert) to between 18 and 225 microplastics/g, comprised of polyethylene terephthalate, polyamide, polypropylene. Snow concentrations varied between 0.1 and 30,000 microplastics/L, containing polyethylene, polyamide, polypropylene. Concentrations within indoor dust varied between 10 and 67,000 microplastics/g, including polyethylene terephthalate, polyethylene, polypropylene. No difference was observed between indoor and outdoor concentrations (microplastics/g) or maximum size (p > 0.05). The minimum size of microplastics were smaller within outdoor dust (p > 0.05). Although comparability is hindered by differing sampling methods, analytical techniques, polymers investigated, spectral libraries and inconsistent terminology, this review provides a synopsis of knowledge to date regarding atmospheric microplastics.

Connection is key when there's no planet B: The need to innovate environmental science communication with transdisciplinary approaches.

As anthropogenic damage to the environment continues worldwide, effective science communication has never been more important. Despite this there are numerous barriers between traditional science communication (e.g. journal articles to news media) and the goal of encouraging more sustainable behaviours. Connections between public groups, science communicators and the environment, are all key to overcome barriers in intergroup communication. It is vital science communication adapts with transdisciplinary approaches to become more effective in its purpose. As such training of environmental science communicators must change. This endeavour will be supported by the enrichment of academic institutions through becoming more active in expediting cooperation between STEM (science, technology, engineering and maths) and HASS (humanities, arts and social science) disciplines. Modern dissemination of misinformation must be tackled with holistic approaches to bridge outgroups and enable the formation of trust.

Initial steps for integrating academic electronic health records into clinical curricula of physical and occupational therapy in the United States: a survey-based observational study.

Training programs must be designed to prepare physical and occupational therapy students to use electronic health records (EHRs) and interprofessional collaboration. This report aims to describe physical and occupational therapy students' perceptions of integrating an academic EHR (AEHR) in their problem-based learning (PBL) curricula in the College of Health Professions, Sacred Heart University, Fairfield, Connecticut, the United States. A paper-based case approach to PBL was adapted by creating patient cases in an AEHR. Students were asked to complete chart reviews and review provider notes to enhance their learning. An online survey was conducted to determine their perceptions of using AEHR from May 2014 to August 2015. Eighty-five students completed the survey, and 88.1% felt that using an AEHR was needed, and 82.4% felt that the additional notes enhanced their understanding of the interdisciplinary team. However, 83.5% reported the AEHR system increased the time needed to extract meaningful information. Incorporating an AEHR into curricula is essential to ensure students are adequately prepared for future patient interactions.

End-to-end system for rapid and sensitive early-detection of SARS-CoV-2 for resource-poor and field-test environments using a $51 lab-in-a-backpack.

COVID-19 has exposed stark inequalities between resource-rich and resource-poor countries. International UN- and WHO-led efforts, such as COVAX, have provided SARS-CoV-2 vaccines but half of African countries have less than 2% vaccinated in their population, and only 15 have reached 10% by October 2021, further disadvantaging local economic recovery. Key for this implementation and preventing further mutation and spread is the frequency of voluntary [asymptomatic] testing. It is limited by expensive PCR and LAMP tests, uncomfortable probes deep in the throat or nose, and the availability of hardware to administer in remote locations. There is an urgent need for an inexpensive "end-to-end" system to deliver sensitive and reliable, non-invasive tests in resource-poor and field-test conditions. We introduce a non-invasive saliva-based LAMP colorimetric test kit and a $51 lab-in-a-backpack system that detects as few as 4 viral RNA copies per µL. It consists of eight chemicals, a thermometer, a thermos bottle, two micropipettes and a 1000-4000 rcf electronically operated centrifuge made from recycled computer hard drives (CentriDrive). The centrifuge includes a 3D-printed rotor and a 12 V rechargeable Li-ion battery, and its 12 V standard also allows wiring directly to automobile batteries, to enable field-use of this and other tests in low infrastructure settings. The test takes 90 minutes to process 6 samples and has reagent costs of $3.5 per sample. The non-invasive nature of saliva testing would allow higher penetration of testing and wider adoption of the test across cultures and settings (including refugee camps and disaster zones). The attached graphical procedure would make the test suitable for self-testing at home, performing it in the field, or in mobile testing centers by minimally trained staff.

Does size matter? Quantification of plastics associated with size fractionated biosolids.

This study investigated the occurrence and contribution of plastic particles associated with size fractionated biosolids to the total concentration in biosolids (treated sewage sludge) samples collected from 20 wastewater treatment plants (WWTP) across Australia. This was achieved through sequential size fractionation of biosolids samples to quantify the mass concentration of 7 common plastics across a range of biosolids size fractions, including below 25 µm which has not been assessed in many previous studies. Quantitative analysis was performed by pressurized liquid extraction followed by pyrolysis coupled to gas chromatography - mass spectrometry. Of the total quantified plastics (Σ7plastics), the greatest proportion (27%) of the total mass were identified in the nominal <25 µm sized biosolids fraction. Polyethylene dominated the polymer mass in every size fraction, even though profiles varied between WWTPs. When comparing the sum of all sites for each sized biosolids fraction, the plurality of the polyethylene, polyvinyl-chloride, polystyrene, polypropylene, polycarbonate, and polyethylene-terephthalate concentrations were associated with the smallest size fraction (<25 µm). We confirm for the first time the presence of plastic particles in biosolids below a size fraction that is not captured by many methods. This is important, because of the potential greater significance of plastics in the low sizes to environmental and human health.

Influence of surface oxidation on the quantification of polypropylene microplastics by pyrolysis gas chromatography mass spectrometry.

The influence of photo-oxidation on the quantification of isotactic polypropylene by Pyrolysis Gas Chromatography/Mass Spectrometry (Pyr-GC/MS) was assessed. Beads (oval shape, ~5 mm) and fragments (irregular shaped, 250-50 µm and 500-1000 µm) were subjected to relatively harsh simulated accelerated weathering conditions (using a filtered xenon-arc reproducing sunlight's full spectrum) for up to 37 and 80 days, respectively. Samples collected (n = 10 replicates for each treatment) at increasing number of weathering days were analysed by Fourier-transform infrared spectroscopy with Attenuated Total Reflection (FTIR-ATR), scanning electron microscopy, and differential scanning calorimetry in order to assess the extent and the rate of degradation. The rate of surface oxidation occurred faster for fragments compared to beads, probably due to their higher surface area. Quantification of the polypropylene trimer (2,4-dimethyl-1-heptene) via double shot Pyr-GC/MS, showed that the signal of the trimer relative to the mass of polypropylene was reduced through weathering with a degradation rate of 1:3 faster for fragments over beads. Signal reduction and carbonyl index were correlated to show that polypropylene with a carbonyl index of ≥13 has a significantly reduced 2,4-dimethyl-1-heptene signal when compared to virgin material. Consequently, the quantification of polypropylene subjected to weathering under harsh conditions may be underestimated by 42% (fragments, carbonyl index: 18) to 49% (beads, carbonyl index: 30) when quantified by Pyr-GC/MS and using virgin polypropylene calibration standards. Pyrolysis at a lower temperature (350 °C) identified six degradation specific markers (oxidation products) that increased in concentration with weathering. Further comparisons between virgin and weathered microplastics may need to be considered to avoid underestimation of microplastic concentrations in future studies.

Plastics in biosolids from 1950 to 2016: A function of global plastic production and consumption.

Plastics are ubiquitous contaminants that leak into the environment from multiple pathways including the use of treated sewage sludge (biosolids). Seven common plastics (polymers) were quantified in the solid fraction of archived biosolids samples from Australia and the United Kingdom from between 1950 and 2016. Six plastics were detected, with increasing concentrations observed over time for each plastic. Biosolids plastic concentrations correlated with plastic production estimates, implying a potential link between plastics production, consumption and leakage into the environment. Prior to the 1990s, the leakage of plastics into biosolids was limited except for polystyrene. Increased leakage was observed from the 1990s onwards; potentially driven by increased consumption of polyethylene, polyethylene terephthalate and polyvinyl chloride. We show that looking back in time along specific plastic pollution pathways may help unravel the potential sources of plastics leakage into the environment and provide quantitative evidence to support the development of source control interventions or regulations.

Quantification of selected microplastics in Australian urban road dust.

Microplastics (1 - 5000 µm) are pervasive in every compartment of our environment. However, little is understood regarding the concentration and size distribution of microplastics in road dust, and how they change in relation to human activity. Within road dust, microplastics move through the environment via atmospheric transportation and stormwater run-off into waterways. Human exposure pathways to road dust include dermal contact, inhalation and ingestion. In this study, road dust along an urban to rural transect within South-East Queensland, Australia was analysed using Accelerated Solvent Extraction followed by pyrolysis Gas Chromatography-Mass Spectrometry (Pyr-GC/MS). Polypropylene, polystyrene, polyethylene terephthalate, polyvinyl chloride, poly (methyl methacrylate) and polyethylene were quantified. Microplastic concentrations ranged from ~0.5 mg/g (rural site) to 6 mg/g (Brisbane city), consisting primarily of polyvinyl chloride (29%) and polyethylene terephthalate (29%). Size fractionation (< 250 µm, 250-500 µm, 500-1000 µm, 1000-2000 µm and 2000-5000 µm) established that the < 250 µm size fraction contained the majority of microplastics by mass (mg/g). Microplastic concentrations in road dust demonstrated a significant relationship with the volume of vehicles (r2 = 0.63), suggesting traffic, as a proxy for human movement, is associated with increased microplastic concentrations in the built environment.

Benchmarking of Molecular Dynamics Force Fields for Solid-Liquid and Solid-Solid Phase Transitions in Alkanes.

Accurate prediction of alkane phase transitions involving solids is needed to prevent catastrophic pipeline blockages, improve lubrication formulations, smart insulation, and energy storage, as well as bring fundamental understanding to processes such as artificial morphogenesis. However, simulation of these transitions is challenging and therefore often omitted in force field development. Here, we perform a series of benchmarks on seven representative molecular dynamics models (TraPPE, PYS, CHARMM36, L-OPLS, COMPASS, Williams, and the newly optimized Williams 7B), comparing with experimental data for liquid properties, liquid-solid, and solid-solid phase transitions of two prototypical alkanes, n-pentadecane (C15) and n-hexadecane (C16). We find that existing models overestimate the melting points by up to 34 K, with PYS and Williams 7B yielding the most accurate results deviating only 2 and 3 K from the experiment. We specially design order parameters to identify crystal-rotator phase transitions in alkanes. United-atom models could only produce a rotator phase with complete rotational disorder, whereas all-atom models using a 12-6 Lennard-Jones potential show no rotator phase even when superheated above the melting point. In contrast, Williams (Buckingham potential) and COMPASS (9-6 Lennard-Jones) reproduce the crystal-to-rotator phase transition, with the optimized Williams 7B model having the most accurate crystal-rotator transition temperature of C15.

Plastic particles in soil: state of the knowledge on sources, occurrence and distribution, analytical methods and ecological impacts.

Increased production and use of plastics has resulted in growth in the amount of plastic debris accumulating in the environment, potentially fragmenting into smaller pieces. Fragments <5 mm are typically defined as microplastics, while fragments <0.1 µm are defined as nanoplastics. Over the past decade, an increasing number of studies have reported the occurrence and potential hazards of plastic particles in the aquatic environment. However, less is understood about plastic particles in the terrestrial environment and specifically how much plastic accumulates in soils, the possible sources, potential ecological impacts, interaction of plastic particles with the soil environment, and appropriate extraction and analytical techniques for assessing the above. In this review, a comprehensive overview and a critical perspective on the current state of knowledge on plastic pollution in the soil environment is provided: detailing known sources, occurrence and distribution, analytical techniques used for identification and quantification and the ecological impacts of particles on soil. In addition, knowledge gaps are identified along with suggestions for future research.

Release of Plastics to Australian Land from Biosolids End-Use.

Plastics are contaminants of emerging concern that can enter the environment from multiple sources, including via land application of treated sewage sludge (biosolids). Biosolids samples collected from 82 wastewater treatment plants (WWTPs) across Australia and covering 34% of the population during census week in 2016 were quantitatively analyzed to estimate the release of seven common plastics. Quantitative analysis was performed by pressurized liquid extraction followed by double-shot microfurnace pyrolysis coupled to gas chromatography mass spectrometry. Ninety nine percent of the samples contained plastics (Σ6plastics) at concentrations of between 0.4 and 23.5 mg/g dry weight (median; 10.4 mg/g dry weight), while polycarbonate was not detected in any sample. Per-capita mass loads of plastics (Σ6plastics) released were between 8 and 877 g/person/year across all investigated WWTPs. Polyethylene was the predominant plastic detected, contributing to 69% of Σ6plastics. Based on the concentrations measured, it was projected that around 4700 metric tons (Mt) of plastics are released into the Australian environment through biosolids end-use each year, equating to approximately 200 g/person/year, which represents 0.13% of total plastics use in Australia. Of this, 3700 Mt of plastics are released to agricultural lands and 140 Mt to landscape topsoil. Our results provide a first quantitative per-capita mass loads and emission estimate of plastic types through biosolids end-use.

A review of the efficacy of tooth bleaching.

UNLABELLED: Current tooth lightening systems use hydrogen peroxide or carbamide peroxide which releases hydrogen peroxide as the bleaching agent. In vitro and in vivo studies, mostly comparing different bleaching systems, have demonstrated the efficacy of vital and non-vital tooth bleaching. Bleaching treatments are affected by a number of factors including the actual cause of tooth discoloration. All in-surgery bleaching agents are chemically activated and, whilst better results are possible with lights, these are not essential. Shade change can be evaluated subjectively and may be observed after only a few nights with Night Guard Vital Bleaching (NGVB). Objective methods of shade evaluation are used in most randomized controlled trials. There are a number of methods used to bleach teeth but NGVB using 10% carbamide peroxide in trays produces the optimal result with the least side-effects. The'inside/outside' bleaching technique using 10% carbamide peroxide is the most effective and safest method of bleaching non-vital teeth. Although more than 90% success has been reported, regression of the colour change is a common problem in vital and non-vital tooth bleaching and retreatment is necessary in many cases, usually after 1-3 years. The overwhelming evidence indicates that tooth bleaching is effective if supervised by a dentist. CLINICAL RELEVANCE: The clinician should be able to inform patients that both vital and non-vital tray bleaching using 10% carbamide peroxide can produce excellent results when supervised. However, shade regression is likely in 1-3 years.

A review of the safety of tooth bleaching.

UNLABELLED: This article considers the safety of tooth bleaching based on a Medline search of clinical, animal and in vitro studies between 1986 and 2007. CLINICAL RELEVANCE: Bleaching is the least invasive option for improving tooth colour compared to alternatives such as crowns and veneers. However, no dental procedure is without risk and the clinician should be aware of the safety issues and adverse effects of tooth bleaching so that patients can be fully informed.