The transient and steady pervaporation of 1-butanol–water mixtures through a poly[1-(trimethylsilyl)-1-propyne] (PTMSP) membrane was studied to observe and elucidate the diffusion phenomena in this high-performing organophilic glassy polymer. Pervaporation was studied in a continuous sequence of experiments under conditions appropriate for the separation of bio-butanol from fermentation broths: feed concentrations of 1.5, 3.0 and 4.5 w/w % of 1-butanol in nutrient-containing (yeast extract) water, temperatures of 37, 50 and 63 °C, and a time period of 80 days. In addition, concentration polarization was assessed. As expected, the total flux and individual component permeabilities declined discernibly over the study period, while the separation factor (average β = 82) and selectivity towards 1-butanol (average α = 2.6) remained practically independent of the process conditions tested. Based on measurements of pervaporation transients, for which a new apparatus and model were developed, we found that the diffusivity of 1-butanol in PTMSP decreased over time due to aging and was comparable to that observed using microgravimetry in pure vapor in 1-butanol. Hence, despite the gradual loss of free volume of the aging polymer, the PTMSP membrane showed high and practically independent selectivity towards 1-butanol. Additionally, a new technique for the measurement and evaluation of pervaporation transients using Fourier transform infrared spectroscopy (FTIR) analysis of permeate was proposed and validated.

In this work, a poly(1-trimethylsilyl-1-propyne) (PTMSP) mixed-matrix membrane was fabricated for the selective removal of 1-butanol from aqueous solutions through pervaporation. Silica nanoparticles (SNPs), which were surface-modified with surfactant hexadecyltrimethylammonium bromide (CTAB), were incorporated into the structure of the membrane. The modified membrane was characterized by thermogravimetry-differential scanning calorimetry (TG-DSC), contact angle measurements, and scanning electron microscope (SEM) analysis. It was found that the surface hydrophobicity of the membrane was improved when compared to neat PTMSP by contact angle measurement. It was confirmed by SEM analysis that a uniform distribution of surface-modified SNPs throughout the PTMSP membrane was achieved. The thermogravimetric analysis detected the thermal degradation of the modified PTMSP at 370 °C, which is comparable to neat PTMSP. The pervaporation measurements showed a maximum separation factor of 126 at 63 °C for 1.5 w/w% 1-butanol in the feed. The maximum total flux of approximately 1.74 mg·cm−2·min−1 was observed with the highest inspected temperature of 63 °C and at the 1-butanol concentration in the feed 4.5 w/w%. The pervaporation transients showed that the addition of the surface-modified SNPs significantly enhanced the diffusivity of 1-butanol in the composite compared to the neat PTMSP membrane. This improvement was attributed to the influence of the well-dispersed SNPs in the PTMSP matrix, which introduced an additional path for diffusivity.

Microplastic fibers (MF) are released from synthetic textiles during washing and end up in the wastewater. Similarly, silver nanoparticles (AgNP), incorporated in textiles as antimicrobial agents, are released in washing machines, also reaching the wastewater treatment plants. Therefore, both MF and AgNP co-exist in the environment, and enter the soil compartment mainly via the application of biosolids. Yet, the combined effect of MF and AgNP has not been studied. Here, we assessed the effects of polyester MF (0.01% DW) on the toxicity of AgNP (32, 100, 320, 1000, 3200 mg Ag/kg) and AgNO3 (12.8, 32, 80, 200, 500 mg Ag/kg) to the earthworm Eisenia andrei and the enchytraeid Enchytraeus crypticus. The exposure to MF caused a decrease in the number of juveniles and changed the biochemical composition of earthworms. Moreover, the presence of MF increased the toxicity of AgNP to earthworm reproduction (EC50 = 165 mg Ag/kg) when compared to AgNP exposure alone (EC50 = 450 mg Ag/kg), but did not alter the toxicity of AgNO3 (EC50 = 40 mg Ag/kg). For enchytraeids, no significant difference in Ag toxicity could be detected when MF was added to the soil for both AgNP and AgNO3. Overall, Ag bioaccumulation was not affected by MF, with the exception of a decrease in earthworm body concentration at the highest Ag soil concentration (3200 mg Ag/kg). Our results suggest that the presence of MF in the soil compartment may be a cause of concern, and that the joint exposure to Ag may be deleterious depending on the Ag form, organism and endpoint. The present work provides the first evidence that a realistic MF concentration in soil lowers AgNP concentration necessary to provoke reproductive impairment in earthworms. The influence of MF on risk assessment of AgNP should be considered.

Pyraclostrobin (Pyr) is one of the most effective fungicides. However, it can degrade via photolysis in water, it is toxic to aquatic life and if inhaled, it has a low solubility in water, that leads to difficulties when applying to plants by spraying. Additionally, the necessity of repeated (weekly) sprays of fungicides when the pathogen growth risk is the highest, such as at the temperature range of 24 to 36 °C and increased humidity of about 95%, leads to loss of efficiency of the fungicide and overdose of chemicals. In the present study, pyraclostrobin was microencapsulated to solve the abovementioned issues. As a core of capsules octadecane (OD) with a melting point of 28 °C was used, thus, the release of pyraclostrobin was controlled via temperature change. Pyraclostrobin-loaded submicrocapsules (PyrSMCs) were characterized using SEM, DLS, TGA/DSC, HPLC, FTIR methods; stimuli-responsivity was tested employing in vitro tests with pathogenic culture (Fungal strain of Pyrenophora teres - CPPF-453) grown in Petri dishes. Toxicity of PyrSMCs to Artemia salina was studied as well. Size of capsules was 200–600 nm along with the presence of bigger capsules with a diameter of 1–4 µm. PyrSMCs showed excellent antifungal effects above the melting point of octadecane. PyrSMCs demonstrated 29 times less toxicity than pyraclostrobin of technical grade. Overall, results show the potential of such capsules to be applied in the agricultural industry for precise agriculture strategies.

No abstract