Boosted micropollutant removal over urchin-like structured hydroxyapatite-incorporated nickel magnetite catalyst via peroxydisulfate activation.

In this work, urchin-like structured hydroxyapatite-incorporated nickel magnetite (NiFe3O4/UHdA) microspheres were developed for the efficient removal of micropollutants (MPs) via peroxydisulfate (PDS) activation. The prepared NiFe3O4/UHdA degraded 99.0 % of sulfamethoxazole (SMX) after 15 min in 2 mM PDS, having a first-order kinetic rate constant of 0.210 min-1. In addition, NiFe3O4/UHdA outperformed its counterparts, i.e., Fe3O4/UHdA and Ni/UHdA, by giving rise to corresponding 3.6-fold and 8.6-fold enhancements in the SMX removal rate. The outstanding catalytic performance can be ascribed to (1) the urchin-like mesoporous structure with a large specific surface area and (2) the remarkable synergistic effect caused by the redox cycle of Ni3+/Ni2+ and Fe2+/Fe3+ that enhances multipath electron transfers on the surface of NiFe3O4/UHdA to produce more reactive oxygen species. Moreover, the effects of several reaction parameters, in this case the initial solution pH, PDS dosage, SMX concentration, catalyst loading, co-existing MPs and humic acid level on the catalytic performance of the NiFe3O4/UHdA + PDS system were systematically investigated and discussed in detail. The plausible catalytic mechanisms in the NiFe3O4/UHdA + PDS system were revealed via scavenging experiments and electron paramagnetic resonance analysis, which indicated a radical (•OH and SO4•-) as the major pathway and a nonradical (1O2) as the minor pathway for SMX degradation. Furthermore, NiFe3O4/UHdA exhibited fantastic magnetically separation and retained good catalytic activity with a low leached ion concentration during the performance of four cycles. Overall, the prepared NiFe3O4/UHdA with outstanding PDS activation could be a promising choice for the degradation of persistent organic pollutants from wastewater.

Parametric studies during the removal of ammonia by membrane contactor with various stripping solutions.

Although membrane contactors (MCs) have been recognized to be an efficient approach for the removal of ammonia from water streams, factors affecting the MCs performance were not clearly investigated. In this study, the effects of stripping solution chemistry (acid types and concentration), feed solution chemistry (pH, temperature, and ammonia concentration), and stages of MCs system have been comprehensively evaluated. Interestingly, the type of stripping solutions significantly affected the removal of ammonia, and the comparative effectiveness were in the order of H3PO4 > H2SO4 > HCOOH. However, the concentration of stripping solutions and ammonia in the feed has little impact to the performance of MCs. Among the feed solution chemistry, pH and temperature were the most crucial factors for ammonia removal in MCs, because the increase of pH and temperature enhanced the free ammonia fraction in the solution and facilitated the mass transfer through pores. At the absorbent concentration of 0.5 M H3PO4, pH of 10, and temperature of 40 °C, single-stage MCs could achieve 51% of ammonia removal within 40 s, and the ammonia removal rate in two-stage MCs reached 90% at the 1.5 min of hydraulic retention time (HRT). The results suggested the superior feasibility of multi-stage MCs system compare to the conventional stripping processes for the removal of ammonia in various waste or wastewater.

Urchin-like structured magnetic hydroxyapatite for the selective separation of cerium ions from aqueous solutions.

In this study, bio-inspired urchin-like structured hydroxyapatite (UHdA) and its magnetic composite (UHdA@Fe3O4) were developed for efficient and easy separation of cerium ions (Ce3+) from aquatic waste streams. UHdA and UHdA@Fe3O4 exhibited superior Ce3+ adsorption capacities of 248.39 and 230.01 mg/g-UHdA respectively, compared to a commercial HdA (141.71 mg/g-HdA) due to their hierarchical mesoporous structure and large specific surface area. The adsorption of Ce3+ to UHdA and UHdA@Fe3O4 were heterogeneous, pseudo-second-order-kinetic, and the rate-limiting step was external mass transfer and intra-particle diffusion. Moreover, thermodynamic studies revealed that the adsorption process was spontaneous and endothermic nature. The high selectivity towards Ce3+ in multi-ionic systems is attributed to the strong affinity between strong Lewis acid (Ce3+) and base (PO43- and OH-) interactions. XRD, FTIR, and XPS analysis demonstrated that the adsorption was mainly attributable to the ion exchange of Ce3+ with Ca2+ and to surface complexation. The desorption of Ce3+ was efficiently accomplished using 0.1 M HNO3. The results suggest that UHdA and UHdA@Fe3O4 could be promising choices for the adsorption and recovery of rare earth elements.

Efficient removal of 17α-ethinylestradiol from secondary wastewater treatment effluent by a biofilm process incorporating biogenic manganese oxide and Pseudomonas putida strain MnB1.

This study proposes a biofilm process to immobilize biogenic manganese oxide (BMO) and Pseudomonas putida MnB1 (BMO-MnB1), which shows excellent synergistic effects for 17α-ethinylestradiol (EE2) from secondary wastewater treatment effluent (WWTE). Modified granular activated carbon (M-GAC) was used as the packing carrier, inoculated with Pseudomonas putida MnB1 and Mn(II) to form the BMO-MnB1 biofilm. Feasibility tests were performed to compare the EE2 removal efficiency with that of the conventional biofilm process (BAC) for heterogeneous microbial communities. Results show that in the BAC, EE2 was removed mainly by adsorption, with biodegradation contributing only slightly to the overall performance. In contrast, the BMO-MnB1 biofilter outperformed the BAC. Furthermore, less than 4% of the total EE2 removed was extracted from the biofilter medium over 150 days of operation, confirming that EE2 was biodegraded by P. putida MnB1 or chemically oxidized by BMO. Our results suggest that BMO-MnB1 biofilm processes have high potential for practical applications in removal of endocrine disrupting compounds from wastewater effluent.

Synergistic effects of biogenic manganese oxide and Mn(II)-oxidizing bacterium Pseudomonas putida strain MnB1 on the degradation of 17 α-ethinylestradiol.

While biogenic manganese oxide (BMO) generated via the oxidation of Mn(II) by the Mn-oxidizing bacteria (MOB) have received attention, the relative roles of biological activity by MOB themselves were not clearly investigated. In this study, the synergistic effects of BMO and MOB Pseudomonas putida strain MnB1 on the degradation of 17α-ethinylestradiol (EE2) was investigated. Experiments with BMO in the presence of P. putida MnB1 showed 15-fold higher removal than that with BMO alone, suggesting that EE2 degradation was mediated by the biological activity of MOB as well as abiotic reaction by BMO. Trapping experiments with pyrophosphate (PP) proved that Mn(III) intermediate formed during the biological process from Mn (II) to Mn (IV) contribute much to the EE2 removal. Also, sharp decreases in EE2 removal were observed when microbial activity was inactivated by heat treatment or sodium azide. From this study, the EE2 removal mechanisms by BMO in the presence P. putida MnB1 are described as follows: (1) abiotic oxidation of EE2 by BMO occurs. (2) P. putida MnB1 indirectly oxidizes EE2 by transferring electrons from the Mn (III) intermediate. (3) P. putida MnB1 continuously re-oxidizes the Mn(II) released from the oxidative degradation of EE2 by BMO, generating new Mn(III)-intermediates or BMO.