Non-thermal plasma activated peroxide and percarbonate for tetracycline and oxytetracycline degradation: Synergistic performance, degradation pathways, and toxicity evaluation.

Tetracycline (TC) and Oxytetracycline (OTC) are common antibiotics increasingly detected in the environment, posing a potential risk to human and aquatic lives. Although conventional methods such as adsorption and photocatalysis are used for the degradation of TC and OTC, they are inefficient in removal efficiency, energy yield, and toxic byproduct generation. Herein, a falling-film dielectric barrier discharge (DBD) reactor coupled with environmentally friendly oxidants (hydrogen peroxide (HPO), sodium percarbonate (SPC), and HPO + SPC) was applied, and the treatment efficiency of TC and OTC was investigated. Experimental results showed that moderate addition of the HPO and SPC exhibited a synergistic effect (SF > 2), significantly improving the antibiotic removal ratio, total organic removal ratio (TOC), and energy yield by more than 50%, 52%, and 180%, respectively. After 10 min of DBD treatment, the introduction of 0.2 mM SPC led to a 100% antibiotic removal ratio and a TOC removal of 53.4% and 61.2% for 200 mg/L TC and 200 mg/L OTC, respectively. Also, 1 mM HPO dosage led to 100% antibiotic removal ratios after 10 min of DBD treatment and a TOC removal of 62.4% and 71.9% for 200 mg/L TC and 200 mg/L OTC, respectively. However, the DBD + HPO + SPC treatment method had a detrimental effect on the performance of the DBD reactor. After 10 min of DBD plasma discharge, the removal ratios for TC and OTC were 80.8% and 84.1%, respectively, when 0.5 mM HPO + 0.5 mM SPC was added. Moreover, principal component and hierarchical cluster analysis confirmed the differences between the treatment methods. Furthermore, the concentration of oxidant-induced in-situ generated ozone and hydrogen peroxide were quantitatively determined, and their indispensable roles during the degradation process were established via radical scavenger tests. Finally, the synergetic antibiotic degradation mechanisms and pathways were proposed, and the toxicities of the intermediate byproducts were evaluated.

Advances of non-thermal plasma discharge technology in degrading recalcitrant wastewater pollutants. A comprehensive review.

With development and urbanization, the amount of wastewater generated due to human activities drastically increases yearly, causing water pollution and intensifying the already worsened water crisis. Although convenient, conventional wastewater treatment methods such as activated sludge, stabilization ponds, and adsorption techniques cannot fully eradicate the complex and recalcitrant contaminants leading to toxic byproducts generation. Recent advancements in wastewater treatment techniques, specifically non-thermal plasma technology, have been extensively investigated for the degradation of complex pollutants in wastewater. Non-thermal plasma is an effective alternative for degrading and augmenting the biodegradability of recalcitrant pollutants due to its ability to generate reactive species in situ. This article critically reviews the non-thermal plasma technology, considering the plasma discharge configuration and reactor types. Furthermore, the influence of operational parameters on the efficiency of the plasma systems and the reactive species generated by the system during discharge has gained significant interest and hence been discussed. Also, the application of non-thermal plasma technology for the degradation of pharmaceuticals, pesticides, and dyes and the inactivation of microbial activities are outlined in this review article. Additionally, optimistic applications involving the combination of non-thermal plasma and catalysts and pilot and industrial-scale projects utilizing non-thermal plasma technology have been addressed. Concluding perceptions on the challenges and future perspectives of the non-thermal technology on wastewater treatment are accentuated. Overall, this review outlines a comprehensive understanding of the non-thermal plasma technology for recalcitrant pollutant degradation from a scientific perspective providing detailed instances for reference.

Influences of cation valence on water absorbency of crosslinked carboxymethyl cellulose.

Anti-drought is a global challenge. The addition of superabsorbent polymers (SAPs) in soil can lower down the water percolation and evaporation. However, the salt-tolerance and repeating water absorbency (RWA) of prepared SAPs have not satisfied the requirements for implementation. This research investigated the influence of cation valence (Na+, Ca2+ and Al3+) on the structural variations of a crosslinked carboxymethyl cellulose (CCMC) using carboxymethyl cellulose (CMC) cross linked by epichlorohydrin (ECH). The results showed that higher addition of NaOH resulted in higher water absorbency (WA) due to the existence of more carboxyl group. The prepared CCMC sample with 5% CMC and 3% NaOH (CCMC53) was a qualified SAP with WA of 969.0 g/g in deionized water. The salt resistance and the hydrophilicity of sample CCMC53 decreased with the increase of cation valence in the solution. The introduction of Na+ resulted in the replacement of H+ from carboxyl group in sample CCMC53-Na. The coordination of carboxyl group and Ca2+ was bidentate chelating and tridentate bridging for carboxyl group and Al3+. The introduction polyvalent cations benefited the stabilization of carboxyl group, however, retarded the swelling ability of sample CCMC53 and hence resulted in lower WACS. The RWA of sample CCMC53 in deionized water and salt solution dropped the most in the first absorption cycle and then reached constant after a few more cycles. It was necessary to control the first swelling degree of SAP in order to keep the RWA at a higher level.

Influences of chemically controlled Ca-bearing minerals in chitosan on Pb2+ removal efficiency.

Highly purified chitosan was generally preferred for heavy metal (HM) removal and the preparation parameters varied largely without any agreement. This study investigated to the influences of chitin with different purities on the HM removal of corresponding chitosan. Sea shrimp waste was used as raw materials and Pb2+ was used as target HM. The results of orthogonal experimental analysis showed that only acid concentration played an important role in the deproteinization and demineralization processes of the chitin preparation under HCl, H2SO4 and CH3COOH treatment. Ca-bearing minerals (CBM) but not free -NH2 group of chitosan played a major role in the removal of Pb2+ from solution. Partly purified chitosan mainly removed Pb2+ by precipitation and then biosorption. The dissociation of Ca2+ from CBM elevated pH value of Pb2+ solution which benefited to precipitation and the formation of NH2-Pb2+. Partly purified chitosan prepared from HCl and CH3COOH treated chitin showed 720-753 mg/g of Pb2+ adsorption at the initial pH value of 6.0; however, highly purified chitosan prepared from HCl treated chitin showed only 45-160 mg/g. Chitosan prepared from H2SO4 treated chitin showed 720-752 mg/g of Pb2+ adsorption. This research found the unexplored information for the industrial application of chitosan with minimum cost but the highest HM removal efficiency.

The effect of Ca-bearing contents in chitosan on Pb 2+, Cd 2+ and Cu 2+ adsorption and its adsorption mechanism.

The preparation of chitosan has been investigated for more than half century; however, the application of chitosan for heavy metal (HM) adsorption is still under research. This study investigated the effects of chitosan with chemically controlled Ca-bearing contents (CBC) on Pb2+, Cd2+ and Cu2+ adsorption in the solution with the initial pH values of 2.10, 4.14 and 6.13. Highly purified chitosan showed the optimum HM adsorption at the initial pH values of 4.14 and 6.13, and the adsorption mechanism was chemisorption involving valence forces through sharing or exchange of electrons between the chitosan and HM ions. Highly purified chitosan prepared from HCl treated chitin only showed effective for Pb2+, however, those prepared from CH3COOH treated chitin showed effective for Pb2+, Cd2+ and Cu2+ adsorption due to a little amount of CBC. The HM adsorption mechanisms of partly purified chitosan were precipitation due to CBC and biosorption. Chitosan with 73% CBC showed the optimum adsorption of Pb2+ (755 mg/g) at an initial pH value of 2.10 while Cd2+ (979 mg/g) and Cu2+ (877 mg/g) at the initial pH values of 4.14 and 6.13. High Ca(OH)2-bearing chitosan prepared from HCl and H2SO4 treated chtin showed the optimum Cd2+ (978 mg/g) and Cu2+ (852 mg/g) adsorption at an initial pH value of 2.10. Biosorption isotherm and kinetics models showed that the adsorption data of Pb2+, Cd2+ and Cu2+ onto the surface of chitosan was well-fitted by Langmuir model and Pseudo-second-order model with correlation coefficient (R2 > 0.95 and R2 > 0.91, respectively). Pseudo-second-order model showed that the adsorption capacity strongly depended on CBC in chitosan and initial pH value of HM solution. It is concluded that the HM adsorption by the prepared chitosan is a chemical process that was supported by CBC of chitosan through elevating solution pH value.

Influences of nitrite on paracetamol degradation in dielectric barrier discharge reactor.

The frequent detection of paracetamol in natural water increased environmental concerns. The dielectric barrier discharge (DBD) technology is an effective paracetamol removing method, however, this research showed that the removal of paracetamol using DBD technology at 30 min dropped from 100% to 53.3% as the initial paracetamol concentration increased from 10 mg/L to 100 mg/L, due to the formation of more competitive intermediate products at higher paracetamol concentration. The removal of TOC was found to be much slower than that of paracetamol, as paracetamol was removed completely after 5 min treatment, the removal rate of TOC was 46.3% after 20 min treatment under 500 W discharge power and 50 mL/min air flow rate. The orthogonal experiment showed that the removal of TOC was significantly influenced by the treatment time, discharge power and recirculating flow rate, while less influenced by the discharge frequency. In the removal process of paracetamol, nitrite ion that generated during DBD treatment reacted with paracetamol to form an intermediate product of 3-nitro-4-acetamidophenol. The presence of nitrite ion retarded the removal of 3-nitro-4-acetamidophenol and thus the TOC, however, the nitrate ion did not. The degradation of paracetamol followed a sequence of 3-nitro-4-acetamidophenol, nitrosophenol/acetamide, N-methylacetamide, acetamide and small molecule organic acids in the DBD reactor, and these intermediates were finally oxidized to CO2, H2O and NO3-.

The effect of electric field intensification at interparticle contacts in microwave sintering.

The nature of microwave sintering cannot be explained in the past and has been generally called microwave effect. Here we show that the E-field intensification is the reason of microwave fast sintering of solid state inorganic compounds. The intensification degree varied with dielectric constant of compound, distance between two particles, angle between the direction of E-field and the normal to the surface at the adjacent point of two spheres. Ultra-high temperature caused by E-field intensification leads to fusing of solid materials at contact zone and enhances the mass transportation. The key to develop a microwave energy-saved sintering method is to control the distance between particles and uniformity of particles instead of the particle size.