Coupling physiochemical adsorption with biodegradation for enhanced removal of microcystin-LR in water.

To innovate the design of water treatment technology for algal toxin removal, this research investigated the mechanisms of cyanotoxin microcystin-LR (MC-LR) removal by a coupled adsorption-biodegradation. Eight types of woody carbonaceous adsorbents with and without Sphingopyxis sp. m6, a MC-LR degrading bacterium, were tested for MC-LR removal in water. All adsorbents showed good adsorption capability, removing 40 % to almost 100 % of the MC-LR (4.5 mg/L) within 48 h in batch experiments. Adding Sphingopyxis sp. m6 continuously promoted MC-LR biological removal, and successfully broke the barrier of adsorption capacity of tested adsorbents, removing >90 % of the MC-LR in most of the coupled adsorption-biodegradation tests, especially for those adsorbents had low physiochemical adsorption capacity. Variance partitioning analysis indicated that mesopore was the dominant contributor to adsorption capacity of MC-LR in pure adsorption treatments, which acted synergistically with electrical conductivity, polarity and total functional groups on the absorbent. Pore structure was the key factor beneficial for the growth of Sphingopyxis sp. m6 (51% contribution) and subsequent MC-LR biological removal rate (80 % contribution). Overall, pinewood-based carbonaceous adsorbents (especially pinewood activated carbon) exhibited the highest adsorption capacity towards MC-LR and provided the most favorable conditions for biological removal of MC-LR, largely because of their high mesopore volume, total functional groups and electric conductivity. The research outcomes not only deepened the quantitative understanding of mechanisms for MC-LR removal by the coupled process, but also provided theoretical basis for future materials' selection and modification during the practical application of coupled process.

Immobilization of Microcystin by the Hydrogel-Biochar Composite to Enhance Biodegradation during Drinking Water Treatment.

Microcystin-LR (MC-LR), the most common algal toxin in freshwater, poses an escalating threat to safe drinking water. This study aims to develop an engineered biofiltration system for water treatment, employing a composite of poly(diallyldimethylammonium chloride)-biochar (PDDA-BC) as a filtration medium. The objective is to capture MC-LR selectively and quickly from water, enabling subsequent biodegradation of toxin by bacteria embedded on the composite. The results showed that PDDA-BC exhibited a high selectivity in adsorbing MC-LR, even in the presence of competing natural organic matter and anions. The adsorption kinetics of MC-LR was faster, and capacity was greater compared to traditional adsorbents, achieving a capture rate of 98% for MC-LR (200 µg/L) within minutes to tens of minutes. Notably, the efficient adsorption of MC-LR was also observed in natural lake waters, underscoring the substantial potential of PDDA-BC for immobilizing MC-LR during biofiltration. Density functional theory calculations revealed that the synergetic effects of electrostatic interaction and π-π stacking predominantly contribute to the adsorption selectivity of MC-LR. Furthermore, experimental results validated that the combination of PDDA-BC with MC-degrading bacteria offered a promising and effective approach to achieve a sustainable removal of MC-LR through an "adsorption-biodegradation" process.

In-Situ H2O2 Cleaning for Fouling Control of Manganese-Doped Ceramic Membrane through Confined Catalytic Oxidation Inside Membrane.

This work presents an effective approach for manganese-doped Al2O3 ceramic membrane (Mn-doped membrane) fouling control by in-situ confined H2O2 cleaning in wastewater treatment. An Mn-doped membrane with 0.7 atomic percent Mn doping in the membrane layer was used in a membrane bioreactor with the aim to improve the catalytic activity toward oxidation of foulants by H2O2. Backwashing with 1 mM H2O2 solution at a flux of 120 L/m2/h (LMH) for 1 min was determined to be the optimal mode for in-situ H2O2 cleaning, with confined H2O2 decomposition inside the membrane. The Mn-doped membrane with in-situ H2O2 cleaning demonstrated much better fouling mitigation efficiency than a pristine Al2O3 ceramic membrane (pristine membrane). With in-situ H2O2 cleaning, the transmembrane pressure increase (ΔTMP) of the Mn-doped membrane was 22.2 kPa after 24-h filtration, which was 40.5% lower than that of the pristine membrane (37.3 kPa). The enhanced fouling mitigation was attributed to Mn doping, in the Mn-doped membrane layer, that improved the membrane surface properties and confined the catalytic oxidation of foulants by H2O2 inside the membrane. Mn3+/Mn4+ redox couples in the Mn-doped membrane catalyzed H2O2 decomposition continuously to generate reactive oxygen species (ROS) (i.e., HO• and O21), which were likely to be confined in membrane pores and efficiently degraded organic foulants.

Fenton cleaning strategy for ceramic membrane fouling in wastewater treatment.

Membrane fouling is an obstacle impeding the wide applications of ceramic membranes and organics are responsible for most of the membrane fouling issues in wastewater treatment. In this study, Fenton cleaning strategy was firstly proposed to clean ceramic membrane fouling in wastewater treatment. Fe2+ efficiently catalyzed fouling cleaning with H2O2 (1.5%) to recover the filterability of ceramic membrane. The maximum ∆TMP recovery (over 99%) was achieved at an optimal Fe2+ dosage of 124 mg/L after 6 hr of immersion cleaning. The total residual membrane fouling resistance decreased gradually from this optimum value as the Fe2+ dosage increased above 124 mg/L. The residual hydraulically reversible fouling resistance accounted for most of the membrane fouling and was basically removed (≤3.0 × 109 m-1) when Fe2+ dosages higher than 124 mg/L were used. The foulants responsible for the formation of a residual hydraulically reversible fouling layer (DOC (dissolved organic carbon), proteins, polysaccharides, EEM (fluorescence excitation-emission matrix spectra), SS (suspended solids), and VSS (volatile suspended solids)) were gradually removed as the Fe2+ dosage increased. These residual organic foulants were degraded from biopolymers (10-200 kDa) to low molecular weight substances (0.1-1 kDa), and the particle size of these residual foulants decreased significantly as a result. The strong oxidation power of hydrogen peroxide/hydroxy radicals towards organic foulants was enhanced by Fe2+. Fe2+ played a significant role in the removal of hydraulically reversible fouling and irreversible fouling from the ceramic membrane. However, Fe2+ (≥124 mg/L) increased the likelihood of forming secondary iron-organics aggregates.

Comparison of long-term ceramic membrane bioreactors without and with in-situ ozonation in wastewater treatment: Membrane fouling, effluent quality and microbial community.

The comparison of long-term ceramic membrane bioreactors (MBRs) without and with in-situ ozonation was investigated in this study in terms of membrane fouling, activated sludge, effluent quality and microbial community in wastewater treatment. The optimal dosage of in-situ ozonation for long-term MBR operation was firstly determined as 5 mg/L (0.66 mg-ozone/g-mixed liquor suspended solid (MLSS)) with the optimal filterability of mixed liquor. During the long-term filtration experiment, MBR-ozone with in-situ ozonation demonstrated its significantly alleviated ceramic membrane fouling performance compared with MBR-control without in-situ ozonation as a result of the enhanced filterability of mixed liquor and organic foulants removal from membrane surface by in-situ ozonation oxidation. Furthermore, ozonation was beneficial to phosphorus removal and the total phosphorus (TP) concentration in effluent of MBR-control (0.82 ±â€¯0.63 mg/L) was >2-fold higher than that of MBR-ozone (0.29 ±â€¯0.41 mg/L). The improved phosphorus removal performance by ozonation was due to the increased abundance of phosphate accumulating bacteria of Candidatus Accumulibacter in activated sludge. However, ozonation was detrimental to nitrogen removal mainly as a result of the inhibition of denitrification with the decreased relative abundance of denitrification genus of Dechloromonas in activated sludge. Overall, ceramic MBR with in-situ ozonation had not only significantly alleviated membrane fouling but also remarkably improved phosphorus removal performance.

Simultaneous and Efficient Capture of Inorganic Nitrogen and Heavy Metals by Polyporous Layered Double Hydroxide and Biochar Composite for Agricultural Nonpoint Pollution Control.

Agricultural nonpoint pollution has been recognized as the main source of aquatic contaminants worldwide, such as inorganic nitrogen (ION) and heavy metals (HMs). It is an important challenge to simultaneously and efficiently immobilize soil ION and HMs in farmland. Herein, we present a polyporous Mg/Fe-layered double hydroxide and biochar composite (Mg/Fe-LDH@biochar) with the efficient coadsorption capacity of ION and HMs for the mitigation of agricultural nonpoint pollution toward aquatic systems. The Mg/Fe-LDH@biochar showed strong adsorption toward ION (i.e., NH4+-N and NO3--N) and HMs (i.e., Cu, Zn, Ni, Pb, and Cd), with maximum capacity of 98.53 mg of NH4+-N/g, 27.09 mg of NO3--N/g, 295.80 of mg Cu/g, 141.70 mg of Zn/g, 75.59 mg of Ni/g, 1264.10 mg of Pb/g, and 126.30 mg of Cd/g, respectively. More attractively, by deionized water extraction, the adsorbed ION on the composite was more easily rereleased, with a desorption percentage of about 42.33 ± 6.87% NO3--N and 1.42 ± 0.78% NH4+-N, than that of HMs (<1.0%). This difference is primarily related with the strength of bonding forces of ION and HMs when adsorbed on Mg/Fe-LDH@biochar, in the sequence of NO3--N (van der Waals force and electrostatic attraction) < NH4+-N (hydrogen bonding) < HMs (ionic/coordinate bonding). Finally, to examine the performance of Mg/Fe-LDH@biochar for practical applications in farmland, column leaching experiments were successfully conducted by stimulated rainfall events. The addition of Mg/Fe-LDH@biochar into soils could greatly reduce the leaching of ION and HMs simultaneously, with reduction ratios of >60, >40, and >90% for NH4+-N, NO3--N, and HMs, respectively, at 3.0% addition. Moreover, there was no leaching risk of Fe ions into the water body from Mg/Fe-LDH@biochar-amended soils.