One-pot hard template synthesis of mesoporous spinel nanoparticles as efficient catalysts for low temperature CO oxidation

Co-Fe, Cu-Cr, and Co-Mn mixed oxide catalysts were prepared using a one-pot hard template synthesis method, and their catalytic performance was investigated before and after the rearrangement of the template. To evaluate the structural properties of the catalysts, various analyses were employed, including the BET, XRD, H₂-TPR, FE-SEM, EDX, and X-ray digital mapping of the elements. The results indicated that the rearrangement of the catalyst structure had a profound effect on the structural and catalytic properties, so that in all three synthesized catalysts, the specific surface and the reducibility increased significantly, and the crystalline structure and morphology of the catalysts changed remarkably. The specific surface area of the CoFe, CuCr, and CoMn catalysts increased from 3.5, 1.1, and 72.9 m²/g to 151.3, 52.8, and 108.0 m²/g, respectively. These structural changes significantly increased the catalytic performance. The results indicated that the 100% conversion temperature of the CoMn catalyst as the optimal sample after rearrangement was reduced from 250 to 125 °C. Also, the stability of the CoMn catalyst in dry and wet conditions was investigated and the results indicated that the presence of water vapor reduced the activity and stability of the catalyst. The activation energy was also calculated on Co-Mn catalyst (59.5 kJ/mol) and the results confirmed that the most probable mechanism for this reaction was the MVK mechanism.

     

Concentrations of cyclic volatile methylsiloxanes in biosolid amended soil,influent, effluent,receiving water,and sediment of wastewater treatment plants in Canada

A comprehensive surveillance program was conducted to determine the occurrence of three cyclic volatile methylsiloxanes (cVMS) octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in environmental compartments impacted by wastewater effluent discharges. Eleven wastewater treatment plants (WWTPs), representative of those found in Southern Ontario and Southern Quebec, Canada, were investigated to determine levels of cVMS in their influents and effluents. In addition, receiving water and sediment impacted by WWTP effluents, and biosolid-amended soil from agricultural fields were also analyzed for a preliminary evaluation of the environmental exposure of cVMS in media impacted by wastewater effluent and solids. A newly-developed large volume injection (septumless head adapter and cooled injection system) gas chromatography – mass spectrometry method was used to avoid contamination originating from instrumental analysis. Concentrations of D4, D5, and D6 in influents to the 11 WWTPs were in the range 0.282–6.69 μg L⁻¹, 7.75–135 μg L⁻¹, and 1.53–26.9 μg L⁻¹, respectively. In general, wastewater treatment showed cVMS removal rates of greater than 92%, regardless of treatment type. The D4, D5, and D6 concentration ranges in effluent were <0.009–0.045 μg L⁻¹, <0.027–1.56 μg L⁻¹, and <0.022–0.093 μg L⁻¹, respectively. The concentrations in receiving water influenced by effluent, were lower compared to those in effluent in most cases, with the ranges <0.009–0.023 μg L⁻¹, <0.027–1.48 μg L⁻¹, and <0.022–0.151 μg L⁻¹ for D4, D5, and D6, respectively. Sediment concentrations ranged from <0.003–0.049 μg g⁻¹ dw, 0.011–5.84 μg g⁻¹ dw, and 0.004–0.371 μg g⁻¹ dw for D4, D5, and D6, respectively. The concentrations in biosolid-amended soil, having values of <0.008–0.017 μg g⁻¹ dw, <0.007–0.221 μg g⁻¹ dw, and <0.009–0.711 μg g⁻¹ dw for D4, D5, and D6, respectively, were lower than those in sediment impacted by wastewater effluent in most cases. In comparison with the no-observed-effected concentrations (NOEC) and IC50 (concentration that causes 50% inhibition of the response) values, the potential risks to aquatic, sediment-dwelling, and terrestrial organisms from these reported concentrations are low.     

Determination of cyclic volatile methylsiloxanes in water,sediment, soil,biota, and biosolid using large-volume injection–gas chromatography–mass spectrometry

Several methods were developed to detect the cyclic volatile methylsiloxanes (cVMSs) including octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) in water, sediment, soil, biota, and biosolid samples. Analytical techniques employed to optimize measurement of this compound class in various matrices included membrane-assisted solvent extraction in water, liquid–solid extraction for sediment, soil, biota, and biosolid samples. A subsequent analysis of the extract was conducted by large-volume injection–gas chromatography−mass spectrometry (LVI−GC−MS). These methods employed no evaporative techniques to avoid potential losses and contamination of the volatile siloxanes. To compensate for the inability to improve detection limits by concentrating final sample extract volumes we used a LVI–GC–MS. Contamination during analysis was minimized by using a septumless GC configuration to avoid cVMS’s associated with septum bleed. These methods performed well achieving good linearity, low limits of detection, good precision, recovery, and a wide dynamic range. In addition, stability of cVMS in water and sediment was assessed under various storage conditions. D4 and D5 in Type-I (Milli-Q) water stored at 4 °C were stable within 29 d; however, significant depletion of D6 (60–70%) occurred only after 3 d. Whereas cVMS in sewage influent and effluent were stable at 4 °C within 21 d. cVMS in sediment sealed in amber glass jars at −20 °C and in pentane extracts in vials at −15 °C were stable during 1 month under both storage conditions.     

Analytical solution to evaluate salt precipitation during CO2 injection in saline aquifers

Carbon dioxide sequestration in deep saline aquifers is a means of reducing anthropogenic atmospheric emissions of CO₂. Among various mechanisms, CO₂ can be trapped in saline aquifers by dissolution in the formation water. Vaporization of water occurs along with the dissolution of CO₂. Vaporization can cause salt precipitation, which reduces porosity and impairs permeability of the reservoir in the vicinity of the wellbore, and can lead to reduction in injectivity. The amount of salt precipitation and the region in which it occurs may be important in CO₂ storage operations if salt precipitation significantly reduces injectivity. Here we develop an analytical model, as a simple and efficient tool to predict the amount of salt precipitation over time and space. This model is particularly useful at high injection velocities, when viscous forces dominate.First, we develop a model which treats the vaporization of water and dissolution of CO₂ in radial geometry. Next, the model is used to predict salt precipitation. The combined model is then extended to evaluate the effect of salt precipitation on permeability in terms of a time-dependent skin factor. Finally, the analytical model is corroborated by application to a specific problem with an available numerical solution, where a close agreement between the solutions is observed. We use the results to examine the effect of assumptions and approximations made in the development of the analytical solution. For cases studied, salt saturation was a few percent. The loss in injectivity depends on the degree of reduction of formation permeability with increased salt saturation. For permeability-reduction models considered in this work, the loss in injectivity was not severe. However, one limitation of the model is that it neglects capillary and gravity forces, and these forces might increase salt precipitation at the bottom of formation particularly when injection rate is low.     

Metabolic responses of Eisenia fetida after sub-lethal exposure to organic contaminants with different toxic modes of action

Nuclear magnetic resonance (NMR) - based metabolomics has the potential to identify toxic responses of contaminants within a mixture in contaminated soil. This study evaluated the metabolic response of Eisenia fetida after exposure to an array of organic compounds to determine whether contaminant-specific responses could be identified. The compounds investigated in contact tests included: two pesticides (carbaryl and chlorpyrifos), three pharmaceuticals (carbamazephine, estrone and caffeine), two persistent organohalogens (Aroclor 1254 and PBDE 209) and two industrial compounds (nonylphenol and dimethyl phthalate). Control and contaminant-exposed metabolic profiles were distinguished using principal component analysis and potential contaminant-specific biomarkers of exposure were found for several contaminants. These results suggest that NMR-based metabolomics offers considerable promise for differentiating between the different toxic modes of action (MOA) associated with sub-lethal toxicity to earthworms.     

Relationship of firm attributes,ownership structure and business network on climate change efforts: evidence from Malaysia

This paper presents a case study of land-use/land-cover (LULC) changes from 1975 to 2014 in the central highlands of Ethiopia and traces out its impact on socioeconomic conditions of the local community in the study area. We used four time series Landsat satellite images, that is, Landsat MSS (1975), Landsat Thematic Mapper (1986), Enhanced Thematic Mapper (2000), and Landsat 8 OLI scenes (2014), to investigate the changes in LULC. In addition, individual interviews with 51 randomly selected households, discussions with focus group and key informants, and field observations were also incorporated for the study. The image classification indicated four categories of LULC classes: Natural forest, eucalyptus plantations, cropland/settlements, and grasslands. Between 1975 and 2014, cropland/settlements and eucalyptus plantations considerably increased, whereas grassland cover drastically decreased. According to the results, the area under cropland/settlements and eucalyptus plantations increased by 62 and 335%, respectively, with 74% concomitant decrease in the area of grasslands in the same period. Survey results showed that deterioration of soil fertility (41.2%) followed by shortage of land (35.3%) is the major constraint for crop production for poor farmers in the study area. However, better-off farmers ranked deterioration of soil fertility (64.7%) followed by lack of credit (17.6%) as priority constraints for crop production. Interviews mainly focused on selected women group revealed that the expansion of eucalyptus in the area greatly curbed the burdens of collecting fuel woods from long distances in the past. The availability of too many religious holidays (on average 16 days/month) directly or indirectly contributes to the current seasonal food shortages of the community. Generally, our results show that the community in the study area is beset with a host of social, economic, and institutional challenges. As a result, majority of the farming households are destitute, unable to make a livelihood from their small plot of land and live in absolute poverty. Therefore, in light of these finding, it is imperative that timely interventions by government and other development stakeholders are needed to come to grips with problems of soil fertility, land-use change, and food insecurity in the study area.     

Portland cement solidified construction waste using MSW leachate and phosphate admixtures

Journal of Material Cycles and Waste Management - Many dumping sites all over the world release leachate into the environment. The primary goal of this study was to convert raw municipal...     

Distribution of hexabromocyclododecane in Detroit River suspended sediments

The distribution of hexabromocyclododecane (HBCD) isomers (alpha, beta and gamma) was determined in Detroit River suspended sediments using liquid chromatography tandem mass spectrometry (LC/MS/MS). Individual isomers of HBCD were measured at concentrations ranging from <0.025 to 1.9 ng/g (dry wt.) for the alpha-isomer, <0.025 to 0.28 ng/g for the beta-isomer, and <0.025 to 2.3 ng/g for the gamma-isomer. Concentrations of total HBCD ranged from <0.075 to 3.7 ng/g. Roughly two-thirds of HBCD profiles in suspended sediments were dominated by the gamma-isomer, and were similar to profiles of commercial technical mixtures. Profiles in the remaining samples were dominated by the alpha-isomer. The beta-isomer was consistently detected at substantially lower levels than the other isomers; this isomer is a minor constituent in the commercial technical mixtures. Seasonal sampling showed significant shifts in the relative ratios of the HBCD isomers. The spatial distribution of HBCD in the Detroit River was similar to other persistent organic pollutants (e.g., PCBs), and showed a strong association with urban/industrial activities in the watershed. However, the highest HBCD concentrations (2.6-3.7 ng/g) were associated with areas of contemporary industrial activity, and were much lower than maximum concentrations of PCBs (2.2 microg/g) found in areas of the Detroit River associated with historical industrial activity.     

Modeling of malachite green adsorption onto novel polyurethane/SrFe12O19/clinoptilolite nanocomposite using response surface methodology and biogeography-based optimization-assisted multilayer neural network

Environmental Science and Pollution Research - This research studied the modeling of malachite green (MG) adsorption onto novel polyurethane/SrFe12O19/clinoptilolite (PU/SrM/CLP) nanocomposite from...     

Methods for selenium removal from contaminated waters: a review

Environmental Chemistry Letters - Worldwide contamination of waters by metals, metalloids, and organometallic pollutants is a major health issue. In particular, the occurrence of the selenium...