Continuous treatment of diethyl hexyl and dibutyl phthalates by fixed-bed reactor: comparison of two esterase bionanocomposites

Financiado para publicación en acceso aberto: Universidade de Vigo/CISUGThe removal of Diethyl hexyl phthalate (DEHP) and Dibutyl phthalate (DBP) is of great importance due to their potential adverse effects on the environment and human health. In this study, two bionanocomposites prepared by immobilization of Bacillus subtilis esterase by crosslinking to halloysite and supported in chitosan and alginate beads were studied and proposed as a green approach. The esterase immobilization was confirmed by physical–chemical characterization. Bionanocomposite using chitosan showed the best degradation levels in batch tests attaining complete degradation of DBP and around 90% of DEHP. To determine the operational stability and efficiency of the system, two fixed bed reactors filled with both bionanocomposites were carried out operating in continuous mode. Chitosan based bionanocomposite showed the best performance being able to completely remove DBP and more than 85% of DEHP at the different flowrates. These results proved the potential of these synthesized bionanocomposites to effectively remove Phthalic Acid Esters.Xunta de Galicia | Ref. ED431C 2021-43Agencia Estatal de Investigación | Ref. PCI2022-13294

Immobilization of esterase from Bacillus subtilis on Halloysite nanotubes and applications on dibutyl phthalate degradation

Dibutyl phthalate (DBP) is one of the listed phthalic acid esters (PAEs) known as the priority toxicants which exhibit carcinogenic and teratogenic properties and is responsible for endocrine disruption. Therefore, its removal has become a matter to tackle with. In this work, the feasibility of DBP degradation by esterase and lipase enzymes obtained from various microorganisms and the immobilization of the most effective in a clayey material were investigated. Esterase from Bacillus subtilis exhibited the highest degradation efficiency reaching a complete degradation. Its immobilization onto halloysite nanotubes (HNTs) by adsorption method was studied by response surface methodology using a central composite design face-centered. The four selected factors that affect the HNT-enzyme composite generation were: pH, adsorption time, enzyme/HNT (E/H) ratio, and adsorption temperature, and the optimal conditions were determined (pH 7, time 360 min, E/H ratio 0.2, temperature 30ºC). Consequently, the activity did not significantly decrease by immobilization, and the adsorption efficiency and relative activity were determined to be 73.15% and 82.7%, respectively. Besides, the immobilization enhanced thermal and storage stability. As for enzyme reusability, after 7 continuous cycles, the composite maintained almost 75% of its initial activity. Both the free enzyme (1 mg/mL) and the composite degraded 100 mg/L DBP with 100% efficiency and several byproducts were detected. Moreover, the composite could be reused for 7 cycles keeping a remarkable catalytic activity. Overall, this study indicated that the HNT-enzyme composite may be used as an effective candidate for remediation of the environmental media contaminated with DBP and other PAEs.Agencia Estatal de Investigación | Ref. PCI2022-132941Xunta de Galicia | Ref. ED431C 2021-43Universidade de Vigo/CISU

Determination of octanol-air partition coefficients and supercooled liquid vapor pressures of PAHs as a function of temperature: Application to gas-particle partitioning in an urban atmosphere

Octanol-air partition coefficients (K-OA) for 14 polycyclic aromatic hydrocarbons (PAHs) were determined as a function of temperature using the gas chromatographic retention time method. log K-OA values at 25 degrees ranged over six orders of magnitude, between 6.34 (acenaphthylene) and 12.59 (dibenz[a,h]anthracene). The determined K-OA values were within factor of 0.7 (dibenz[a,h]anthracene) to 15.1 (benz[a]anthracene) of values calculated as the ratio of octanol-water partition coefficient to dimensionless Henry's law constant. Supercooled liquid vapor pressures (P-L) of 13 PAHs were also determined using the gas chromatographic retention time technique. Activity coefficients in octanol calculated using K-OA and P-L ranged between 3.2 and 6.2 indicating near-ideal solution behavior

The first countrywide monitoring of selected POPs: Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and selected organochlorine pesticides (OCPs) in the atmosphere of Turkey.

Atmospheric levels of 43 PCBs, 22 OCPs, and 14 PBDEs were determined in 16 cities at urban and rural sites by passive sampling to generate the first large-scale nationwide dataset of POP residues in Turkey\u27s atmosphere. Sampling campaign was performed from May 2014 to April 2015 with three-month sampling periods at locations on east-west and north-south transects through the country to investigate seasonal and spatial variations, including long range atmospheric transport (LRAT). Factor analysis was conducted to infer on the potential sources. Overall average Σ43PCBs concentration was 108 ± 132 pg/m3. PCB-118 (26.3 ± 44.6 pg/m3) was the top congener, and penta-CBs had the highest contribution with 54.3%. ΣDDTs had the highest annual mean concentration with 134 ± 296 pg/m3 among the OCP groups among which the highest concentration compound was p\u27p-DDE (97.6 ± 236 pg/m3). Overall average concentration of Σ14PBDEs was 191 ± 329 pg/m3 with the highest contribution from BDE-190 (42%). Comparison of OCPs and PCBs concentrations detected at temperatures which were above and below annual average temperature indicated higher concentrations in the warmer periods, hence significance of secondary emissions for several OCPs and Σ43PCBs, as well as inference as LRAT from secondary emissions. The first nationwide POPs database constructed in this study, point to current use, local secondary emissions, and LRAT for different individual compounds, and indicate the need for regular monitoring

The first countrywide monitoring of selected POPs: Polychlorinated biphenyls (PCBs), polybrominated diphenyl ethers (PBDEs) and selected organochlorine pesticides (OCPs) in the atmosphere of Turkey.

Atmospheric levels of 43 PCBs, 22 OCPs, and 14 PBDEs were determined in 16 cities at urban and rural sites by passive sampling to generate the first large-scale nationwide dataset of POP residues in Turkey\u27s atmosphere. Sampling campaign was performed from May 2014 to April 2015 with three-month sampling periods at locations on east-west and north-south transects through the country to investigate seasonal and spatial variations, including long range atmospheric transport (LRAT). Factor analysis was conducted to infer on the potential sources. Overall average Σ43PCBs concentration was 108 ± 132 pg/m3. PCB-118 (26.3 ± 44.6 pg/m3) was the top congener, and penta-CBs had the highest contribution with 54.3%. ΣDDTs had the highest annual mean concentration with 134 ± 296 pg/m3 among the OCP groups among which the highest concentration compound was p\u27p-DDE (97.6 ± 236 pg/m3). Overall average concentration of Σ14PBDEs was 191 ± 329 pg/m3 with the highest contribution from BDE-190 (42%). Comparison of OCPs and PCBs concentrations detected at temperatures which were above and below annual average temperature indicated higher concentrations in the warmer periods, hence significance of secondary emissions for several OCPs and Σ43PCBs, as well as inference as LRAT from secondary emissions. The first nationwide POPs database constructed in this study, point to current use, local secondary emissions, and LRAT for different individual compounds, and indicate the need for regular monitoring