Synthesis and performance evaluation of novel soybean oil-based plasticisers for polyvinyl chloride (PVC)

Novel bio-based plasticisers for polyvinyl chloride (PVC) are a significant and growing area of interest. These compounds aim to replace toxic and petrochemical additives in commonly used plastic products. Plasticisers can comprise as much as 50% of the total mass of the PVC product. Epoxidised soybean oil (ESBO) is a commercially available bio-based plasticiser that is typically used at lower levels than traditional phthalates in PVC compounds because it does not show equivalent performance to existing phthalate plasticisers. Four derivatives of ESBO have been synthesised through reaction at the epoxide rings. These compounds have been evaluated in PVC formulations and compared to current petrochemical plasticisers, as well as ESBO. The product of methoxy polyethylene glycol and ESBO shows good plasticising ability, giving a PVC compound with higher tensile strength and elongation than dioctyl phthalate (DOP) and a lower glass transition temperature (Tg) than with the use of ESB

A comparative assessment of the use of suitable analytical techniques to evaluate plasticizer compatibility

The evaluation of novel phthalate-free plasticisers for PVC formulations is hindered by the lack of a reliable quantitative method for testing plasticizer exudation from PVC formulations. Two methods of improving upon the ASTM D3291 exudation test have been trialed using ATR-FTIR and GC–MS. The results of these methods are compared alongside a study of the glass transition temperatures (Tg) by dynamic mechanical analysis (DMA). FTIR is found to be unsuitable for determining plasticizer exudation as the method is not sufficiently sensitive to detect small changes in plasticizer distribution. Carbonyl peak positions in unstressed samples are instead investigated to determine the strength of interaction between the plasticisers and PVC chain. GC–MS is successfully used to quantify plasticizer exudation that could not be observed visually or by FTIR. Furthermore, these methods show limited correlation to each other, which highlights the importance of testing multiple aspects of compatibility when developing novel plasticisers for use in PVC

An investigation into the use of < 38 µm fraction as a proxy for < 10 µm road dust particles

It is well documented that a large portion of urban particulate matters is derived from road dust. Isolating particles of RD which are small enough to be inhaled, however, is a difficult process. In this study, it is shown for the first time that the < 38 µm fraction of road dust particles can be used as a proxy for road dust particles < 10 µm in bioaccessibility studies. This study probed similarities between the < 10 and < 38µm fractions of urban road dust to show that the larger of the two can be used for analysis for which larger sample masses are required, as is the case with in vitro analysis. Road dust, initially segregated to size < 38 µm using sieves, was again size segregated to < 10 µm using water deposition. Both the original < 38 µm and the separated < 10 µm fractions were then subject to single particle analysis by SEM–EDX and bulk analysis by ICP-OES for its elemental composition. Dissolution tests in artificial lysosomal fluid, representative of lung fluid, were carried out on both samples to determine % bioaccessibility of selected potentially harmful elements and thus probe similarities/differences in in vitro behaviour between the two fractions. The separation technique achieved 94.3% of particles < 10 µm in terms of number of particles (the original sample contained 90.4% as determined by SEM–EDX). Acid-soluble metal concentration results indicated differences between the samples. However, when manipulated to negate the input of Si, SEM–EDX data showed general similarities in metal concentrations. Dissolution testing results indicated similar behaviour between the two samples in a simulated biological fluid

A scoping study of component-specific toxicity of mercury in urban road dusts from three international locations

This scoping study presents an investigation of the total and bioaccessible mercury concentrations in road dust (RD) from three international urban sites, where a one-off sampling campaign was conducted at each. This was done to address the hypothesis that the matrix in which mercury is found influences its ability to become accessible to the body once inhaled. For that purpose, the samples were analysed for total and pulmonary bioaccessible mercury and the data compared to the chemical structure of individual particles by SEM. The results obtained from this study suggest that a high mercury content does not necessarily equate to high bioaccessibility, a phenomenon which could be ascribed to the chemical character of the individual particles. It was found that the Manchester samples contained more pulmonary soluble mercury species (as determined by elemental associations of Hg and Cl) in comparison to the other two samples, Curitiba, Brazil, and Johannesburg, South Africa. This finding ultimately underlines the necessity to conduct a site-specific in-depth analysis of RD, to determine the concentration, chemical structure and molecular speciation of the materials within the complex matrix of RD. Therefore, rather than simply assuming that higher bulk concentrations equate to more significant potential human health concerns, the leaching potential of the metal/element in its specific form (for example as a mineral) should be ascertained. The importance of individual particle behaviour in the determination of human health risk is therefore highlighted

Active microbial ecosystem in glacier basal ice fuelled by iron and silicate comminution‐derived hydrogen

The basal zone of glaciers is characterized by physicochemical properties that are distinct from firnified ice due to strong interactions with underlying substrate and bedrock. Basal ice (BI) ecology and the roles that the microbiota play in biogeochemical cycling, weathering, and proglacial soil formation remain poorly described. We report on basal ice geochemistry, bacterial diversity (16S rRNA gene phylogeny), and inferred ecological roles at three temperate Icelandic glaciers. We sampled three physically distinct basal ice facies (stratified, dispersed, and debris bands) and found facies dependent on biological similarities and differences; basal ice character is therefore an important sampling consideration in future studies. Based on a high abundance of silicates and Fe-containing minerals and, compared to earlier BI literature, total C was detected that could sustain the basal ice ecosystem. It was hypothesized that C-fixing chemolithotrophic bacteria, especially Fe-oxidisers and hydrogenotrophs, mutualistically support associated heterotrophic communities. Basal ice-derived rRNA gene sequences corresponding to genera known to harbor hydrogenotrophic methanogens suggest that silicate comminution-derived hydrogen can also be utilized for methanogenesis. PICRUSt-predicted metabolism suggests that methane metabolism and C-fixation pathways could be highly relevant in BI, indicating the importance of these metabolic routes. The nutrients and microbial communities release from melting basal ice may play an important role in promoting pioneering communities establishment and soil development in deglaciating forelands

Elemental Composition of PM2.5 and PM10 and Health Risks Assessment in the Industrial Districts of Chelyabinsk, South Ural Region, Russia

Air pollution impacts all populations globally, indiscriminately and has site-specific variation and characteristics. Airborne particulate matter (PM) levels were monitored in a typical industrial Russian city, Chelyabinsk in three destinations, one characterized by high traffic volumes and two by industrial zone emissions. The mass concentration and trace metal content of PM2.5 and PM10 were obtained from samples collected during four distinct seasons of 2020. The mean 24-h PM10 ranged between 6 and 64 μg/m3. 24-h PM2.5 levels were reported from 5 to 56 μg/m3. About half of the 24-h PM10 and most of the PM2.5 values in Chelyabinsk were higher than the WHO recommendations. The mean PM2.5/PM10 ratio was measured at 0.85, indicative of anthropogenic input. To evaluate the Al, Fe, As, Cd, Co, Cr, Cu, Mn, Ni, Pb, and Zn concentration in PM2.5 and PM10, inductively coupled plasma mass spectrometry (ICP-MS) was used. Fe (337–732 ng/m3) was the most abundant component in PM2.5 and PM10 samples while Zn (77–206 ng/m3), Mn (10–96 ng/m3), and Pb (11–41 ng/m3) had the highest concentrations among trace elements. Total non-carcinogenic risks for children were found higher than 1, indicating possible health hazards. This study also presents that the carcinogenic risk for As, Cr, Co, Cd, Ni, and Pb were observed higher than the acceptable limit (1 × 10−6)

ZIF-8-derived Fe-C catalysts: relationship between structure and catalytic activity toward the oxygen reduction reaction

The oxygen reduction reaction (ORR) activity of carbonized ZIF-8 (CZ) and its Fe-doped derivatives, CZ-A (doped with ammonium iron (II) sulphate) and CZ-B (doped with iron (II) acetate), were examined in both acidic (0.5 M H2SO4) and basic (0.1 M KOH) electrolytes using a rotating disk electrode setup. These data show that the ORR activity of the Fe-doped catalysts is higher than that of pure CZ, with a higher activity in basic than acidic electrolyte. Extensive materials characterization highlights important differences in the sample crystallinity, morphology, porosity, and chemical composition as a function of the deployed precursor. The performance of the prepared catalysts is also impacted by the Fe precursor selection, highlighting the importance of such synthetic parameters in controlling the density and identify of Fe-Nx active sites. These results demonstrate the potential application of Fe-doped carbonized ZIF-8 catalysts for the ORR in basic electrolyte and offer important knowledge for the future design of non-precious metal fuel cell electrocatalysts

EXPRESS: Atomic Absorption Spectrometry Methods to Access the Metal Solubility of Aerosols in Artificial Lung Fluid

Recent studies to quantify the health risks that fine particulate matter with anaerodynamic lessthan 2.5 micrometers (PM2.5) poseuse in vitro approaches. One of these approaches is to incubate PM2.5in artificial lysosomal fluid for a given period at body temperature. These body fluids used have a high ionic strength and as such can be challenging samples to analyzewith atomic spectroscopy techniques. AsPM2.5isaprimary healthhazard because it is tiny enough to penetrate deep into the lungsand could, in addition, dissolve in the lung fluid it is important to quantify elements of toxic and/or carcinogenic concerns, reliably and accurately. Sophisticated instrumentation and expensive pre-treatment of challenging samples are not always available, especially in developing countries. Toevaluatethe applicability of GFAAS without Zeeman correction capability to detect trace quantities of heavy metals leached from PM2.5on to artificial lungfluid, uni-and multivariate approaches have been used for optimization purposes. The limits of quantification, LOQ,obtained by theoptimizedmethod were:2μgL-1(Cu), 3μg L-1(Cr), 1μg L-1(Mn) and 10μg L-1(Pb). The addition/recovery experiments had amean accuracy of: (Cu) 99 ± 7%; 110± 8% (Cr); 95 ± 9% (Mn) and 96 ± 11% (Pb). The average soluble fractions of PM2.5incubated in artificial lysosomal fluid (ALF)for 1 hour were:1.2 0.01ng m-3Cu, 0.40.01ng m-3Cr,0.60.01ng m-3Mnand4.8 0.03ng m-3Pb.Using historical elemental 2averagesof PM2.5 in Curitiba(Cu 3.3 ng m-3, Cr 2.1 ng m-3, Mn 6.1 ng m-3, Pb 21 ng m-3), the percentage bioaccessibility were determined to beCu 38%; Cr 20%; Mn 10%; and Pb 23%.The elemental values of the atmospheric soluble fraction of Cu, Cr and,Mn were below the inhalation risk concentrations.However, for Pb, the atmospheric soluble fraction exceeded the inhalation unit risk of 0.012 ng m-3.This robust and straightforward GF AASmethod is pivotal for low and middle-income countries were most air pollution adverse effects occur andestablished lower-costtechnologies are likelyunavailable

Dynamic model to predict the association between air quality, COVID-19 cases, and level of lockdown

Studies have reported significant reductions in air pollutant levels due to the COVID-19 outbreak worldwide due to global lockdowns. Nevertheless, all of the reports are limited compared to data from the same period over the past few years, providing mainly an overview of past events, with no future predictions. Lockdown level can be directly related to the number of new COVID-19 cases, air pollution, and economic restriction. As lockdown status varies considerably across the globe, there is a window for mega-cities to determine the optimum lockdown flexibility. To that end, firstly, we employed four different Artificial Neural Networks (ANN) to examine the compatibility to the original levels of CO, O3, NO2, NO, PM2.5, and PM10, for São Paulo City, the current Pandemic epicenter in South America. After checking compatibility, we simulated four hypothetical scenarios: 10%, 30%, 70%, and 90% lockdown to predict air pollution levels. To our knowledge, ANN have not been applied to air pollution prediction by lockdown level. Using a limited database, the Multilayer Perceptron neural network has proven to be robust (with Mean Absolute Percentage Error ∼ 30%), with acceptable predictive power to estimate air pollution changes. We illustrate that air pollutant levels can effectively be controlled and predicted when flexible lockdown measures are implemented. The models will be a useful tool for governments to manage the delicate balance among lockdown, number of COVID-19 cases, and air pollution