Interest in soil contamination has been growing in recent years due to the ongoing degradation of soil environments. Therefore, the development of remediation techniques and the study of contaminant sorption and migration are areas of intense research. In this study, the authors sought to evaluate the scenario of co-contamination of a loamy sand soil by multiple heavy metals. To that end, the sorption and transport of five metals-Cr, Pb, Cd, Cu and Zn-was evaluated using representative samples of a soil from the north of Portugal. The tests were conducted in batch and continuous systems using single-and multiple-metal acid solutions to evaluate the effect of metal competition. In accordance with the type of assay-batch or continuous-Langmuir or Convection Dispersion Two-Site Nonequilibrium models were adjusted to explain the sorption/transport data. FTIR analyses were performed on the final samples of the continuous systems. Generally, the results revealed good fitting of the tested models for the metals in competitive and noncompetitive scenarios, with the exception of Zn that was originally present in soil samples at higher concentrations. As expected, the influence of competition was observed in both batch and continuous systems, but with different tendencies. The FTIR spectra also revealed a strong influence of clay minerals and organic matter on the sorption of the metals.
In this study, 1-methylimidazolium hydrogen sulfate, [HMIM]HSO 4 , ionic liquid, was successfully applied as a catalyst in the biodiesel production through the esterification reaction of oleic acid with methanol. A response surface methodology (RSM) known as Box-Behnken Design (BBD) was applied to optimize the main experimental reaction conditions, using a set of 27 experiments. This optimization was based on the maximization of both the conversion of oleic acid and the Fatty Acid Methyl Esters (FAME) content of the obtained biodiesel samples. It was concluded that the two most relevant parameters for both the conversion and the FAME content were the molar ratio between oleic acid and methanol and the catalyst dosage. Accordingly to the model, the optimum condition for the maximum conversion was determined as being 8 h, 110 ± 2°C, 15:1 M ratio methanol/oleic acid and a catalyst dosage of 15 wt%, resulting in a 95% conversion and for the maximum FAME content were 8 h, 110 ± 2°C, 14:1 M ratio and a catalyst dosage of 14 wt%, leading to a FAME content of 90%. The kinetics of the esterification reaction was also evaluated, and the experimental results were well described using a third-order reaction model. The kinetic parameters were experimentally determined, and the value of the activation energy was 6.8 kJ/mol and the pre-exponential factor was 0.0765 L 2 .mol −2 .min −1 confirming that the ionic liquid, [HMIM]HSO 4 , is a good alternative for replacing traditional catalysts for biodiesel production through esterification reaction.
Novel results concerning the inverse vulcanization of sulfur using reversible addition-fragmentation chain transfer (RAFT) polymerization are here reported. It is shown that RAFT polymerization can be used to carry out this cross-linking process, with the additional possibility to extend the reaction time from a few minutes as with classical free radical polymerization (FRP) to several hours. Higher control on viscosity and processability of the synthesized networks, as well as, the implementation of semibatch feed policies during cross-linking are important advantages of the RAFT process here explored comparatively to the FRP inverse vulcanization. Using cyclic voltammetry, it was assessed the electrochemical activity of the synthesized sulfur-rich polymer networks. It is shown that the fundamental electrochemical activity of the elemental sulfur was preserved in the produced materials. Testing of electrochemical cells assembled with lithium in the anode and different sulfur based materials in the cathode, including the synthesized RAFT networks, is also shown. The results here presented highlight the new opportunities introduced by reversible-deactivation radical polymerization mechanisms on the control of the synthesis process and in the design of such advanced materials and show also that many potential derivatizing possibilities can be achieved.
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