Traceable determination of metal composition of tyres using tandem ICP-MS and benchmarking of emissions inventories.

Non-exhaust emissions are becoming of increasing significance with respect to total particulate matter (PM) concentrations in ambient air. Of particular interest is the metal content of this PM since metallic compounds are well known to have toxic effects on human health and the environment. In this study, 'bottom-up' annual tyre wear emission rates were estimated and compared to top-down' emissions declared by the UK; it was calculated that between 14 and 25 tonnes of Zn entered the atmosphere in PM10 in 2020. The emission rates were estimated using a cost-effective, simple but robust validated method for analysis of the metals in tyres using tandem inductively coupled plasma mass spectrometry (ICP-MS/MS) for the first time, involving minimal offline sample preparation. This method was applied to five different tyre makes and brands, all available for sale in the UK, and the uncertainty of each measurement was determined. Traceability was ensured in all methods and novel validation techniques were applied due to lack of available reference materials. Zn was found to be the largest metal component in all tyres with a mass fraction of approximately 10 mg g-1. The mean mass fractions of metals in the tyres decreased in the order of Zn > Al > Fe > Mg > Ti > Pb > Cu > Ba > Ni. Significant differences in composition were found between the five tyres. The relative expanded uncertainties of the metals measurements ranged from 4 to 21%, with elements of higher mass fraction resulting in lower uncertainties. These findings will contribute to assessing current and future air quality challenges and will help to inform regulation surrounding non-exhaust emissions.

Performances and limits of Bag-Valve-Device for pre-oxygenation and manual ventilation: A comparative bench and cadaver study.

INTRODUCTION: Bag-Valve-Device (BVD) is the most frequently used device for pre-oxygenation and ventilation during cardiopulmonary resuscitation (CPR). A minimal expired fraction of oxygen (FeO2) above 0.85 is recommended during pre-oxygenation while insufflated volume (VTi) should be reduced during manual ventilation. The objective was to compare the performances of different BVD in simulated conditions. METHODS: Nine BVD were evaluated during pre-oxygenation: spontaneous breathing patients were simulated on a test lung (mild and severe conditions). FeO2 was measured with and without positive end-expiratory pressure (PEEP). CO2 rebreathing was evaluated. Then, manual ventilation was performed by 36 caregivers (n = 36) from three hospitals on a specific manikin; same procedure was repeated by 3 caregivers (n = 3) on two human cadavers with three of the nine BVD: In non-CPR scenario and during mechanical CPR with Interrupted Chest Compressions strategy (30:2). RESULTS: Pre-oxygenation: FeO2 was lower than 0.85 for three BVD in severe condition and for two BVD in mild condition. FeO2 was higher than 0.85 in eight of nine BVD with an additional PEEP valve (PEEP 5 cmH2O). One BVD induced CO2 rebreathing. Manual ventilation: For non-CPR manual ventilation, mean VTi was within the predefined lung protective range (4-8 mL/kg PBW) for all BVD on the bench. For CPR manual ventilation, mean VTi was above the range for three BVD on the bench. Similar results were observed on cadavers. CONCLUSIONS: Several BVD did not reach the FeO2 required during pre-oxygenation. Manual ventilation was significantly less protective in three BVD. These observations are related to the different BVD working principles.

A robust regression analysis method to determine the significance of trends in concentrations of heavy metals in UK ambient air and improve network design and emission inventories.

A novel application of the Theil-Sen robust regression method for determining the temporal trends in the concentration of heavy metals in UK ambient air over the period 2005-2020 is presented and compared to other regression methods. We have demonstrated improvements over non-robust methods of regression, proving the ability to tease out trends that are small with respect to the variability of the concentration measurement. The method is used to identify, in general, large and significant trends in the concentrations of Ni, As, Pb and V over the period 2005-2020, either across the UK as a whole or at groupings of site classifications in the UK. These trends have been compared to trends in emission data determined in the same manner. Although the results for most metals provide confidence that the UK metal network of monitoring sites is successful in appropriately capturing changes in emissions, a key finding of this work is the disagreement between trends in measured concentrations and emissions for Cu, Mn and Ni, for which we suggest improvements in future network design. The results also indicate that UK emission data for V should be reviewed, as we propose that the rate of reduction of V emissions is likely to have been overestimated.

Correspondence on "An International Study Evaluating Elemental Analysis".

This Correspondence provides a brief commentary on a recent ACS Central Science article that evaluated the performance of different laboratories in elemental analysis and suggests that a broader conclusion should be drawn instead, recognizing the benefits of metrology and the international quality infrastructure.

Dynamics in the ordered and disordered phases of barocaloric adamantane.

High-entropy order-disorder phase transitions can be used for efficient and eco-friendly barocaloric solid-state cooling. Here the barocaloric effect is reported in an archetypal plastic crystal, adamantane. Adamantane has a colossal isothermally reversible entropy change of 106 J K-1 kg-1. Extremely low hysteresis means that this can be accessed at pressure differences less than 200 bar. Configurational entropy can only account for about 40% of the total entropy change; the remainder is due to vibrational effects. Using neutron spectroscopy and supercell lattice dynamics calculations, it is found that this vibrational entropy change is mainly caused by softening in the high-entropy phase of acoustic modes that correspond to molecular rotations. We attribute this difference in the dynamics to the contrast between an 'interlocked' state in the low-entropy phase and sphere-like behaviour in the high-entropy phase. Although adamantane is a simple van der Waals solid with near-spherical molecules, this approach can be leveraged for the design of more complex barocaloric molecular crystals. Moreover, this study shows that supercell lattice dynamics calculations can accurately map the effect of orientational disorder on the phonon spectrum, paving the way for studying the vibrational entropy, thermal conductivity, and other thermodynamic effects in more complex materials.

Falling nickel concentrations in ambient air in South Wales - 50 years of progress.

Measurement of the composition of ambient air has become increasingly widespread over the last 50 years as the detrimental health effects of some air pollutants have become clearer and requirements for these measurements has been embedded in national and international legislation. The aim of this has been not only to assess exposure of the general population to air pollutants but also to assess the effectiveness of abatement strategies to reduce emissions of these pollutants at source. With a rich industrial heritage, the Swansea Valley (South Wales, UK) has long been associated with the refining and production of metal products, especially nickel. Despite a decline in output during the latter part of the twentieth century there is still sufficient activity to prompt a requirement for targeted air monitoring in the area. This is most important for nickel where there is a local history of measured concentrations exceeding legislative target values. This work demonstrates the effectiveness of nickel emissions abatement strategies over the last 50 years by tracking the falling air concentration of nickel over this period. It also demonstrates how the monitoring network in the Swansea Valley has expanded over this time and become significantly more sensitive to nickel emissions. The data presented represents a significant public health achievement - it is likely that the exposure to nickel in air of the population in the Swansea Valley has decreased more than 100-fold over the last 50 years - and reflects the progress in regulation, industrial efficiency, emissions abatement technology and air quality monitoring science achieved during this period.

Early antibiotic therapy is associated with a lower probability of successful liberation from mechanical ventilation in patients with severe acute exacerbation of chronic obstructive pulmonary disease.

BACKGROUND: While antibiotic therapy is advocated to improve outcomes in acute exacerbation of chronic obstructive pulmonary disease (AECOPD) whenever mechanical ventilation is required, the evidence relies on small studies carried out before the era of widespread antibiotic resistance. Furthermore, the impact of systematic antibiotic therapy on successful weaning from mechanical ventilation was never investigated accounting for the competitive risk of death. The aim of the study was to assess whether early antibiotic therapy (eABT) increases successful mechanical ventilation weaning probability as compared to no eABT, in patients with AECOPD without pneumoniae, using multivariate competitive risk regression. METHODS: Retrospective analysis of patients admitted in 2 intensive care units (ICU) from 2012 to 2020 for AECOPD without pneumonia and requiring mechanical ventilation. eABT was defined as any anti-bacterial chemotherapy introduced during the first 24 h after ICU admission. The primary outcomes were the adjusted subdistribution hazard ratio (SHR) of the probability of being successfully weaned from mechanical ventilation (i.e. non-invasive and invasive ventilation) according to eABT status and accounting for the competitive risk of death. RESULTS: Three hundred and ninety-one patients were included, of whom 66% received eABT. eABT was associated with a lower probability of successful liberation from mechanical ventilation when accounting for the competing risk of death in multivariate analyses (SHR 0.71 [95% confidence interval, 0.57-0.89], p < 0.01), after adjustment with covariates of disease severity. This association was present in all subgroups except in patients under invasive mechanical ventilation on ICU day-1, in patients with ICU day-1 worst PaCO2 > 74 torr (median value) and in patients with a documented bacterial bronchitis at ICU admission. Ventilator-free days at day 28, ICU-free days at day 28 and invasive mechanical ventilation-free days at day 28, were significantly lower in the eABT group, while there was no significant difference in mortality at day 28 between patients who received eABT and those who did not. CONCLUSIONS: eABT was independently associated with a lower probability of being successfully weaned from mechanical ventilation, suggesting that the clinician decision to overrule systematic administration of eABT was not associated with a detectable harm in AECOPD ICU patients without pneumonia.

Progress in pre-treatment and extraction of organic and inorganic pollutants by layered double hydroxide for trace-level analysis.

Continuous release of pollutants into the environment poses serious threats to environmental sustainability and human health. For trace-level analysis of pollutants, layered double hydroxide (LDH) is an attractive option to impart enhanced sorption capability and sensitivity toward pollutants because of its unique layered structure, tunable interior architecture, high anion-exchange capacities, and high porosity (e.g., Zn/Cr LDH/DABCO-IL, Ni/Al LDH, CS-Ni/Fe LDH, SDS-Fe3O4@SiO2@Mg-Al LDH, Boeh/Mg/Al LDH/pC, and Fe@NiAl LDH). In concert with the well-defined analytical methodologies (e.g., HPLC and GC), the LDH materials can be employed to detect trace-level targets (e.g., as low as âˆ¼ 20 fg/L for phenols) in aqueous environments. This review highlights LDH as a promising material for pre-treatment of a variety of organic and inorganic target pollutants in complex real matrices. Challenges and future requirements for research into LDH-based analytical methods are also discussed.

Mesoporous silica imprinted carbon dots for the selective fluorescent detection of triclosan.

A molecularly imprinted fluorescence sensor built as a mesoporous structured silica imprinted layer on the surface of carbon dots (CDs@m-MIP) was employed for the selective detection of triclosan (TRI). The fluorescence of this CDs@m-MIP was affected sensitively and selectively by TRI via an electron transfer-induced fluorescence quenching mechanism with a detection limit of TRI at 1.08 nM (range 1.72-138 nM) under the optimum setup (e.g., pH, response time, and CDs@m-MIP dose). This approach was used successfully to detect TRI in real water samples (e.g., sewage, river, and tap water). The recoveries of TRI were satisfactory in spiked river and tap water (in 94.7-99.5 %). The outcome of this research is thus expected to help develop highly efficient fluorescent sensing systems towards diverse hazardous compounds including TRI.

Construction of novel luminescent thermometers based on dual-emission centers of rare-earth and bismuth ions.

Optical thermometry based on fluorescence intensity ratio (FIR) technology has several advantages for industrial and medical applications such as remote signaling, non-invasiveness, and excellent spatial resolution. Here, an approach to the construction of luminescent thermometers is proposed based on high-temperature solid-state reactions through doping of rare earth (RE) elements (e.g., samarium (Sm3+) or europium (Eu3+)) into Ca2Y0.97Bi0.03SbO6 (CYBS) phosphors. The tuning of the CYBS:Eu3+ and CYBS:Sm3+ ratios in the phosphors provided a wide range of color changes from purplish blue to red and from purplish blue to pink, respectively. The superiority of optical thermometer is validated by higher values of absolute sensitivity (Sa) and relative sensitivity (Sr). As such, both phosphors exhibit excellent temperature sensing performance with Sa/Sr values (at 483 K) of 4.945 × 10-2/0.968 × 10-2 K-1 (CYBS:0.05Eu3+) and 2.964 × 10-2/0.864 × 10-2 K-1 (CYBS:0.05 Sm3+). Thus, RE-doped CYBS materials with color tuning properties and superior temperature sensing performance are recommended for the construction of novel luminescent optical thermometers.

Advances in surface plasmon resonance-based biosensor technologies for cancer biomarker detection.

Surface plasmon resonance approach is a highly useful option to offer optical and label-free detection of target bioanalytes with numerous advantages (e.g., low-cost fabrication, appreciable sensitivity, label-free detection, and outstanding accuracy). As such, it allows early diagnosis of cancer biomarkers to monitor tumor progression and to prevent the recurrence of oncogenic tumors. This work highlights the recent progress in SPR biosensing technology for the diagnosis of various cancer types (e.g., lung, breast, prostate, and ovarian). Further, the performance of various SPR biosensors is also evaluated in terms of the basic quality assurance criteria (e.g., limit of detection (LOD), selectivity, sensor response time, and reusability). Finally, the limitations and future challenges associated with SPR biosensors are also discussed with respect to cancer biomarker detection.

Plant-based remediation of air pollution: A review.

Humans face threats from air pollutants present in both indoor and outdoor environments. The emerging role of plants in remediating the atmospheric environment is now being actively investigated as a possible solution for this problem. Foliar surfaces of plants (e.g., the leaves of cotton) can absorb a variety of airborne pollutants (e.g., formaldehyde, benzene, trimethylamine, and xylene), thereby reducing their concentrations in indoor environments. Recently, theoretical and experimental studies have been conducted to offer better insights into the interactions between plants and the surrounding air. In our research, an overview on the role of plants in reducing air pollution (often referred to as phytoremediation) is provided based on a comprehensive literature survey. The major issues for plant-based research for the reduction of air pollution in both outdoor and indoor environments are discussed in depth along with future challenges. Analysis of the existing data confirms the effectiveness of phytoremediation in terms of the absorption and purification of pollutants (e.g., by the leaves and roots of plants and trees), while being controlled by different variables (e.g., pore characteristics and planting patterns). Although most lab-scale studies have shown that plants can effectively absorb pollutants, it is important for such studies to reflect the real-world conditions, especially with the influence of human activities. Under such conditions, pollutants are to be replenished continually while the plant surface area to ambient atmosphere volume ratio vastly decreases (e.g., relative to lab-based experiments). The replication of such experimental conditions is the key challenge in this field of research. This review is expected to offer valuable insights into the innate ability of various plants in removing diverse pollutants (such as formaldehyde, benzene, and particulate matter) under different environmental settings.

Adsorption of environmental contaminants on micro- and nano-scale plastic polymers and the influence of weathering processes on their adsorptive attributes.

Increases in plastic-related pollution and their weathering can be a serious threat to environmental sustainability and human health, especially during the present COVID-19 (SARS-CoV-2 coronavirus) pandemic. Planetary risks of plastic waste disposed from diverse sources are exacerbated by the weathering-driven alterations in their physical-chemical attributes and presence of hazardous pollutants mediated through adsorption. Besides, plastic polymers act as vectors of toxic chemical contaminants and pathogenic microbes through sorption onto the 'plastisphere' (i.e., plastic-microbe/biofilm-environment interface). In this review, the effects of weathering-driven alterations on the plastisphere are addressed in relation to the fate/cycling of environmental contaminants along with the sorption/desorption dynamics of micro-/nano-scale plastic (MPs/NPs) polymers for emerging contaminants (e.g., endocrine-disrupting chemicals (EDCs), polycyclic aromatic hydrocarbons (PAHs), polychlorinated biphenyls (PCBs), pharmaceuticals and personal care products (PPCPs), and certain heavy metals). The weathering processes, pathways, and mechanisms governing the adsorption of specific environmental pollutants on MPs/NPs surface are thus evaluated in relation to the physicochemical alterations based on several kinetic and isotherm studies. Consequently, the detailed evaluation on the role of the complex associations between weathering and physicochemical properties of plastics should help us gain a better knowledge with respect to the transport, behavior, fate, and toxicological chemistry of plastics along with the proper tactics for their sustainable remediation.

Magnesium/aluminum layered double hydroxides intercalated with starch for effective adsorptive removal of anionic dyes.

In this research, the adsorptive performance of a starch-magnesium/aluminum layered double hydroxide (S-Mg/Al LDH) composite was investigated for different organic dyes in single-component systems by conducting a series of batch mode experiments. S-Mg/Al LDH composite showed preferential adsorption of anionic dyes than cationic dyes. The marked impact of key process variables (e.g., contact time, adsorbent dosage, pH, and temperature) on its adsorption was investigated. Multiple isotherms, kinetics, and thermodynamic models were applied to describe adsorption behavior, diffusion, and uptake rates of the organic dyes over S-Mg/Al LDH composite. A better fitting of the non-linear Langmuir model reflects the predominance of monolayered adsorption of dye molecules on the composite surface. Partition coefficients (mg g-1 µM-1) for S-Mg/Al LDH were observed in the following descending order: Amaranth (665) > Tartrazine (186) > Sunset yellow (71) > Eosin yellow (65). Furthermore, comparative evaluation of the adsorption enthalpy, entropy, and Gibbs free energy values indicates that the adsorption process is spontaneous and exothermic. S-Mg/Al LDH composite maintained a stable adsorption/desorption recycling process over six consecutive cycles with the advantages of low cost, chemical/mechanical stability, and easy recovery. The results of this study are expected to expand the application of modified LDHs toward wastewater treatment.

Redefinition of the Mole in the Revised International System of Units and the Ongoing Importance of Metrology for Accurate Chemical Measurements.

This Feature highlights the role of metrology, the science of measurement, in maintaining the infrastructure we all rely on for accurate chemical measurements. In particular, the recent change to the definition of the mole, the unit of chemistry, is explained.

Hollow porous molecularly imprinted polymers as emerging adsorbents.

Hollow porous molecularly imprinted polymers (HPMIPs) are identified as promising adsorbents with many advantageous properties (e.g., large number of imprinted cavities, highly accessible binding sites, controllable pore structure, and fast mass transfer). Because of such properties, HPMIPs can exhibit improved binding capacity and kinetics to make analyte molecules readily interact with a greater number of recognition sites on the imprinted shell. This review highlights the synthesis and utility of HPMIPs as adsorbents to cover diverse targets of interest (e.g., endocrine disrupting chemicals, pharmaceuticals, pesticides, and heavy metal ions). The overall potential of HPMIPs is thus discussed in the context of analytical chemistry with particular focus on the efficient extraction of trace-level targets from complex matrices.

Dual-template magnetic molecularly imprinted polymer-based sorbent for simultaneous and selective detection of phenolic endocrine disrupting compounds in foodstuffs.

In this research, an efficient (94.9-99.4%) and fast (5 min) method has been developed and validated for simultaneous identification and quantification of phenolic endocrine disrupting compounds with an emphasis on bisphenol A (BPA) and 4-cumylphenol (4-CP) in food stuffs using a dual-template magnetic, molecularly-imprinted polymer (dt-MMIP). The dt-MMIP was synthesized by a sol-gel method using Fe3O4@SiO2 (as the core) and BPA and 4-CP (as templates). The dt-MMIP was coupled with magnetic solid phase extraction to simultaneously detect BPA and 4-CP in food samples. BPA was measured from bottled water and fruit juice samples samples at 0.36 and 0.24 ng mL-1, respectively, while 4-CP in those samples was 0.33 and 0.16 ng mL-1, respectively. Their detection limits were estimated as 0.04 and 0.05 ng mL-1, respectively. The developed dt-MMIP method was highly reproducible, while maintaining a good cyclability up to 20 cycles.

Environmental fate, ecotoxicity biomarkers, and potential health effects of micro- and nano-scale plastic contamination.

In recent decades, the quantity of plastic waste products has increased tremendously. As plastic wastes are released into the environment, they exert harmful effects on biota and human health. In this work, a comprehensive review is offered to describe the physical and chemical characteristics of microplastics and nanoplastics in relation to their fate, microbial ecology, transport, and ecotoxic behavior. Present discussion is expanded further to cover the biochemical, physiological, and molecular mechanisms controlling the environmental fate, ecotoxicity, and human health hazards of micro- and nanoplastics. The risks of their exposure to microbes, plants, animals, and human health are also reviewed with special emphasis. Finally, a direction for future interdisciplinary research in materials and polymer science is also discussed to help control the pollution caused by micro- and nanoplastics.