Removal Of Sulfonamide Antibiotics Research Articles

Enhanced removal of sulfonamide antibiotics in water using high-performance S-nZVI/BC derived from rice straw.

Sulfonamide antibiotics (SAs) are widely used in the biomedical field but pose an environmental risk as ecotoxic pollutants. Developing eco-friendly methods to degrade SAs into harmless compounds is crucial. In this work, biochar (BC) was prepared from rice straw via pyrolysis and used to support S-nZVI, thereby forming the S-nZVI/BC composites. The results show high SAs removal efficiency (up to 98.3%) at optimal Fe/C and Fe/S molar ratios of 3:1 and 50:1, respectively, with strong tolerance to coexisting ions. Furthermore, the effectiveness of S-nZVI/BC(Fe3/C1, Fe50/S1) sample was validated using five real wastewaters, and the results showed consistent performance, stability and reusability. Mechanistic studies revealed that S-nZVI/BC synergized with persulfate to enhance the reactivity of sulfate-free radical (SO4-·) and Fe2+. The degradation pathways of SAs, involving electrophilic substitution and nucleophilic attack, were elucidated by density functional theory (DFT) calculations. These insights were instrumental in comprehending the degradation mechanism of SAs. Additionally, the degradation dynamics of ten SAs were further analyzed using quantitative structure-activity relationship (QSAR) models and principal component analysis (PCA). Hence, this work highlights the potential of S-nZVI/BC for industrial wastewater treatment, providing insights into the degradation mechanisms and pathways of SAs.

Mechanism of microplastics promoting sulfamethoxazole biodegradation in activated sludge as revealed by DNA-stable isotope probing

Microplastics (MPs) often coexist with sulfonamide antibiotics (SAs) in the activated sludge of wastewater treatment plants (WWTPs). Microbial degradation is a crucial pathway for SAs removal in the activated sludge, though its response to MPs still yet to be disclosed. Here, we combined DNA-stable isotope probing (DNA-SIP), PICRUSt and MENA techniques to explore the impact of MPs on the microbial biodegradation of sulfamethoxazole (SMX) in the activated sludge. DNA-SIP revealed 20 genera were responsible for the SMX degradation in the activated sludge, with 13 of these genera being firstly linked with sulfonamide biodegradation. The potential SMX-degrading bacteria showed complex synergistic interaction with the other microbes. Eight degradation pathways were constructed based on the nine identified SMX-related degradation genes. MPs addition enhanced the SMX biodegradation by altering the structure of degrading microbes, increasing their relative abundance and promoting the synergistic interactions between potential SMX-degrading bacteria and other microbes in activated sludge. Besides, genes related to abundant energy production and biofilm formation were involved in SMX degradation in the activated sludge with MPs. Our study reveals the MPs influence on SMX biodegradation in activated sludge, and disclose the potential underlying mechanisms, which will benefit the regulation on antibiotic removal in WWTPs.

Removal of sulfonamide antibiotics by constructed wetland substrate with NaOH-modified corn straw biochar under different operating conditions

This study examined the elimination of sulfonamide antibiotics (SAs) by constructed wetland substrates with NaOH-modified corn straw biochar and assessed the impact of environmental conditions on the effectiveness of SAs removal. The study demonstrated that the constructed wetland substrate with NaOH-modified biochar significantly eliminated eight SAs, with a removal rate of over 94 %. During the removal process, the intermediates will undergo regeneration of the parent compounds under low DO concentrations. This was based on the linear stepwise regression analysis and Geodetector models. The results showed that SA types COD, NH4+-N, TN, and DO had a stronger influence. The dominant bacteria in the constructed wetland system were mainly affected by antibiotic concentration, DO, NH4+-N and NO3–-N, which affected the removal of antibiotics. Overall, the constructed wetland substrate with NaOH-modified corn straw biochar can be effectively employed as an ecological method for eliminating SAs from the environment.

Direct Electron Transfer-Driven Nontoxic Oligomeric Deposition of Sulfonamide Antibiotics onto Carbon Materials for In Situ Water Remediation.

The rising in situ chemical oxidation (ISCO) technologies based on polymerization reactions have advanced the removal of emerging contaminants in the aquatic environment. However, despite their promise, uncertainties persist regarding their effectiveness in eliminating structurally complex contaminants, such as sulfonamide antibiotics (SAs). This study elucidated that oligomerization, rather than mineralization, predominantly governs the removal of SAs in the carbon materials/periodate system. The amine groups in SAs played a crucial role in forming organic radicals and subsequent coupling reactions due to their high f- index and low bond orders. Moreover, the study highlighted the robust adhesion of oligomers to the catalyst surface, facilitated by enhanced van der Waals forces and hydrophobic interactions. Importantly, plant and animal toxicity assessments confirmed the nontoxic nature of oligomers deposited on the carbon material surface, affirming the efficacy of carbon material-based ISCO in treating contaminated surface water and groundwater. Additionally, a novel classification approach, Δlog k, was proposed to differentiate SAs based on their kinetic control steps, providing deeper insights into the quantitative structure-activity relationship (QSAR) and facilitating the selection of optimal descriptors during the oligomerization processes. Overall, these insights significantly enhance our understanding of SAs removal via oligomerization and demonstrate the superiority of C-ISCO based on polymerization in water decontamination.

Zr-based multivariate metal-organic framework for rapid extraction of sulfonamide antibiotics from water and food samples

Based on multiple ligands strategy, a series of multivariate metal organic frameworks (MTV-MOFs) named as PCN-224-DCDPSx were prepared using one-pot solvothermal method to extract and remove sulfonamide antibiotics (SAs). The pore structure and adsorption performance can be further regulated by modulating the doping ratios of medium-tetra(4-carboxylphenyl) porphyrin and 4,4′-dicarboxydiphenyl sulfones. The MTV-MOFs of PCN-224-DCDPS1.0 possesses very large specific surface area (1625 m2/g). Using PCN-224-DCDPS1.0 as sorbent, a dispersive solid-phase extraction method was developed to extract and preconcentrate SAs from water, eggs, and milk prior to high performance liquid chromatography analysis. The limits of detection of method were determined between 0.17 and 0.27 ng/mL with enrichment factors ranging 214–327. The adsorption can be finished within 30 s, and the recovery rate remains above 80 % after 10 repeated uses. The adsorption capacities of sorbent were determined from 300 to 621 mg/g for sulfadiazine, sulphapyridine, sulfamethoxydiazine, sulfachlorpyridazine, sulfabenzamide, and sulfadimethoxine. The adsorption mechanisms were investigated and can be attributed to π-π interactions, hydrogen bonds, and electrostatic interactions. This work represents a method for preparation of MTV-MOFs and uses as sorbent for extraction and enrichment of trace pollutants from complex samples.

Protocatechuic acid enhanced the selective degradation of sulfonamide antibiotics in Fe(III)/peracetic acid process under actually neutral pH conditions

The practical application of the Fe-catalyzed peracetic acid (PAA) processes is seriously restricted due to the need for narrow pH working range and poor anti-interference capacity. This study demonstrates that protocatechuic acid (PCA), a natural and eco-environmental phenolic acid, significantly enhanced the removal of sulfonamide antibiotics in Fe(III)/PAA process under actually neutral pH conditions (6.0–8.0) by complexing Fe(III). With sulfamethoxazole (SMX) as the model contaminant, the pseudo-first-order rate constant of SMX elimination in PCA/Fe(III)/PAA process was 63.5 times higher than that in Fe(III)/PAA process at pH 7.0, surpassing most of the previously reported strategies-enhanced Fe-catalyzed PAA processes (i.e., picolinic acid and hydroxylamine etc.). Excluding the primary contribution of reactive species commonly found in Fe-catalyzed PAA processes (e.g., •OH, R-O•, Fe(IV)/Fe(V) and 1O2) to SMX removal, the Fe(III)-peroxy complex intermediate (CH3C(O)OO-Fe(III)-PCA) was proposed as the primary reactive species in PCA/Fe(III)/PAA process. DFT theoretical calculations indicate that CH3C(O)OO-Fe(III)-PCA exhibited stronger oxidation potential than CH3C(O)OO-Fe(III), thereby enhancing SMX removal. Four potential removal pathways of SMX were proposed and the toxicity of reaction solution decreased with the removal of SMX. Furthermore, PCA/Fe(III)/PAA process exhibited strong anti-interference capacity to common natural anions (HCO3−, Cl−and NO3−) and humic acid. More importantly, the PCA/Fe(III)/PAA process demonstrated high efficiency for SMX elimination in actual samples, even at a trace Fe(III) dosage (i.e., 5 μM). Overall, this study provided a highly-efficient and eco-environmental strategy to remove sulfonamide antibiotics in Fe(III)/PAA process under actually neutral pH conditions and to strengthen its anti-interference capacity, underscoring its potential application in water treatment.

Cooperation among nitrifying microorganisms promotes the irreversible biotransformation of sulfamonomethoxine

Ammonia-oxidizing microorganisms, including AOA (ammonia-oxidizing archaea), AOB (ammonia-oxidizing bacteria), and Comammox (complete ammonia oxidization) Nitrospira, have been reported to possess the capability for the biotransformation of sulfonamide antibiotics. However, given that nitrifying microorganisms coexist and operate as communities in the nitrification process, it is surprising that there is a scarcity of studies investigating how their interactions would affect the biotransformation of sulfonamide antibiotics. This study aims to investigate the sulfamonomethoxine (SMM) removal efficiency and mechanisms among pure cultures of phylogenetically distinct nitrifiers and their combinations. Our findings revealed that AOA demonstrated the highest SMM removal efficiency and rate among the pure cultures, followed by Comammox Nitrospira, NOB, and AOB. However, the biotransformation of SMM by AOA N. gargensis is reversible, and the removal efficiency significantly decreased from 63.84 % at 167 h to 26.41 % at 807 h. On the contrary, the co-culture of AOA and NOB demonstrated enhanced and irreversible SMM removal efficiency compared to AOA alone. Furthermore, the presence of NOB altered the SMM biotransformation of AOA by metabolizing TP202 differently, possibly resulting from reduced nitrite accumulation. This study offers novel insights into the potential application of nitrifying communities for the removal of sulfonamide antibiotics (SAs) in engineered ecosystems.

Removal of sulfonamide antibiotics by non-free radical dominated peroxymonosulfate oxidation catalyzed by cobalt-doped sulfur-containing biochar from sludge

The reuse of activated sludge as a solid waste is severely underutilized due to the limitations of traditional treatment and disposal methods. Given that, the sulfur-containing activated sludge catalyst doped with cobalt (SK-Co(1.0)) was successfully prepared by one-step pyrolysis and calcinated at 850 ℃. The generation of CoSx was successfully characterized by X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), indicating that the sulfur inside the sludge was the anchoring site for the externally doped cobalt. Cobalt (Ⅱ) (Co2+), as the main adsorption site for peroxymonosulfate(PMS), formed a complex (SK-Co(1.0)-PMS* ) and created the conditions for the generation of surface radicals. The SK-Co(1.0)/PMS system showed high degradation efficiency and apparent rate constants for Sulfamethoxazole (SMX) (91.56% and 0.187 min−1) and Sulfadiazine (SDZ) (90.73% and 0.047 min−1) within 10 min and 30 min, respectively. Three sites of generation of 1O2, which played a dominant role in the degradation of SMX and SDZ in the SK-Co(1.0)/PMS system, were summarized as：sulfur vacancies (SVs), the Co3+/Co2+ cycles promoted by sulfur(S) species, oxygen-containing functional groups (C-O). The degradation mechanisms and pathways had been thoroughly investigated using DFT calculations. In view of this, a new idea for the resource utilization of activated sludge solid waste was provided and a new strategy for wastewater remediation was proposed.

Comparison of the effectiveness of UV, UV/VUV photolysis, ozonation, and ozone/UV processes for the removal of sulfonamide antibiotics

UV (254 nm) and UV/VUV (254/185 nm) photolysis, ozonation, and O3/UV combination were investigated and compared for the transformation of two sulfonamide (SAs) antibiotics, sulfamethazine (SMT) and sulfamethoxypyridazine (SMP). Change in toxicity, the effect of bacteria growth inhibition of the treated solutions, and the cost-efficiency of the methods were studied. In UV/VUV radiated solutions, the formation of •OH results in the doubled transformation rate. The relative contribution of various ROS (•OH, 1O2, O2•−) to the transformations were also investigated in the case of UV and UV/VUV photolysis. Both SAs can be eliminated ten times faster during ozonation than UV photolysis; but conversion via ozonation is associated with the formation of products with low reactivity to ozone and has biological effects. The O3/UV process did not enhance the transformation rate but positively affected mineralization and significantly decreased the ecotoxicity of the treated solutions. Ozonation was cost-effective, but O3/UV is a much safer technology to minimize environmental impacts because it effectively reduces the ecotoxicity and the bacterial growth inhibition effect of the treated solution. The observed differences between SMT and SMP are primarily related to the transformation of the N-containing rings. Our results showed a correlation between the reactivity of the N-containing groups of SAs, the rate of mineralization, and the change in ecotoxicity and antibacterial effect and emphasized the need for toxicological characterization of the treated samples. The removal of parent compounds is not sufficient to avoid the release of toxic substances into the environment.

Optimization of removal of sulfonamide antibiotics by magnetic nanocomposite from water samples using central composite design

The present study aimed to remove sulfonamide antibiotics from water samples using magnetic Fe3O4-bentonite nanocomposite (Fe3O4-Bt) as an adsorbent. The adsorbent has a surface area of 74.27 m2 g-1, a pore size of 87.53 nm, and a pore volume of 0.146 cm3 g-1. A central composite design (CCD) matrix was employed to model and optimize the process. The optimal conditions for removing sulfonamide antibiotics were determined using Fe3O4-Bt adsorbent at an antibiotic concentration of 20 mg L-1, the amount of nanoparticles of 0.23 g, pH of 6, and ultrasonication time of 17 min. The reusability study of the Fe3O4-Bt adsorbent showed that the Fe3O4-Bt could be used five times in adsorption/desorption processes. Also, applying the Fe3O4-Bt adsorbent on real samples revealed that Fe3O4-Bt adsorbent could remove sulfonamide antibiotics in the range of 86.85–97.47% with RSD (n = 5) < 4.

Removal of sulfonamide antibiotics by a sonocatalytic Fenton-like reaction: Efficiency and mechanisms

With the widespread use of sulfonamide antibiotics (SAs), SAs are detected as residues in aquatic environments, posing a serious threat to human life and safety. Because of their high water solubility, fast transmission rate, and strong antibacterial properties, the safe disposal of SAs has become a key constraint for water quality assurance. Therefore, an ultrasound (US)-assisted zero-valent iron (ZVI)/persulfate (PS) system was proposed to explore the rapid and effective degradation of SAs. Comparative experiments were performed to study the removal of sulfadiazine (SDZ) by US, ZVI, PS, US/ZVI, US/PS, ZVI/PS, and US-ZVI/PS systems, respectively. Experimental results indicated that the highest removal efficiency of SDZ was ahieved in US-ZVI/PS system (97.4%), which were 2–44 times higher than that in other systems. Furthermore, the degradation efficiency of five typical SAs was achieved over 95%, demonstrating the effectiveness of the US ZVI/PS system for SAs removal. Also, quantum chemical computations for potential reactive sites of SAs and intermediate product detection by HPLC‒MS/MS were performed. The radical attack on active sites of SAs, such as N atom (number 7), was the main reason for SAs removal in US-ZVI/PS system. Besides, the common degradation pathways of six typical SAs were defined as S–N bond cleavage, C–N bond cleavage, benzene ring hydroxylation, aniline oxidation, and R substituent oxidation. Interestingly, the unique pathway of “SO2 group extraction” was observed in the degradation of six-membered ring SAs. Therefore, the US-ZVI/PS system is a promising and cost-effective method for the removal of SAs and other refractory pollutants.

Degradation of Sulfamethoxazole by Manganese(IV) Oxide in the Presence of Humic Acid: Role of Stabilized Semiquinone Radicals.

In this work, we demonstrate for the first time the abatement of sulfamethoxazole (SMX) induced by stabilized ortho-semiquinone radicals (o-SQ•-) in the MnO2-mediated system in the presence of humic acid. To evaluate the performance of different MnO2/mediator systems, 16 mediators are examined for their effects on MnO2 reactions with SMX. The key role of the bidentate Mn(II)-o-SQ• complex and MnO2 surface in stabilizing SQ•- is revealed. To illustrate the formation of the Mn(II)-o-SQ• complex, electron spin resonance, cyclic voltammetry, and mass spectra were used. To demonstrate the presence of o-SQ• on the MnO2 surface, EDTA was used to quench Mn(II)-o-SQ•. The high stability of o-SQ•- on the MnO2 surface is attributed to the higher potential of o-SQ•- (0.9643 V) than the MnO2 surface (0.8598 V) at pH 7.0. The SMX removal rate constant by different stabilized o-SQ• at pH 7.0 ranges from 0.0098 to 0.2252 min-1. The favorable model is the rate constant ln (kobs,7.0) = 6.002EHOMO(o-Qred) + 33.744(ELUMO(o-Q) - EHOMO(o-Qred)) - 32.800, whose parameters represent the generation and reactivity of o-SQ•, respectively. Moreover, aniline and cystine are competitive substrates for SMX in coupling o-SQ•-. Due to the abundance of humic constituents in aquatic environments, this finding sheds light on the low-oxidant-demand, low-carbon, and highly selective removal of sulfonamide antibiotics.

Deciphering of sulfonamide biodegradation mechanism in wetland sediments: from microbial community and individual populations to pathway and functional genes

Figuring out the comprehensive metabolic mechanism of sulfonamide antibiotics (SA) is critical to improve and optimize SA removal in the bioremediation process, but relevant studies are still lacking. Here, an approach integrating metagenomic analysis, degraders’ isolation, reverse transcriptional quantification and targeted metabolite determination was used to decipher microbial interactions and functional genes’ characteristics in SA-degrading microbial consortia enriched from wetland sediments. The SA-degrading consortia could rapidly catalyze ipso-hydroxylation and subsequent reactions of SA to achieve the complete mineralization of sulfadiazine and partial mineralization of the other two typical SA (sulfamethoxazole and sulfamethazine). Paenarthrobacter, Achromobacter, Pseudomonas and Methylobacterium were identified as the primary participants for the initial transformation of SA. Among them, Methylobacterium could metabolize the heterocyclic intermediate of sulfadiazine (2-aminopyrimidine), and the owning of sadABC genes (SA degradation genes) made Paenarthrobacter have relatively higher SA-degrading activity. Besides, the coexistence of sadABC genes and sul1 gene (SA resistance gene) gave Paenarthrobacter a dual resistance mechanism to SA. The results of reverse transcription quantification further demonstrated that the activity of sadA gene was related to the biodegradation of SA. Additionally, sadABC genes were relatively conserved in a few Microbacteriaceae and Micrococcaceae SA-degraders, but the multiple recombination events caused by densely nested transposase encoding genes resulted in the differential sequence of sadAB genes in Paenarthrobacter genome. These new findings provide valuable information for the selection and construction of engineered microbiomes.

Effects of polypropylene microplastics on multiple sulfonamide removals by the Fenton process

We investigated the effects of polypropylene microplastics (MPPs) on removing four sulfonamide antibiotics (SAs) through the Fenton process. The interference of MPPs on SAs removal highly depended on the attached ions and polar groups. While the original MPPs showed a negligible effect, MPPs pre-treated with Na2S2O3, NaClO, NaOH, NaHCO3, FeSO4, Fe(NO3)3, methanol, tert-butanol, humic acids, O3, and UV inhibited the removal ratio by 11% to 70% due to the consumption of hydroxyl radicals by the aged MPPs. H2SO4-treated MPPs promoted 9% SAs removals due to increased adsorption removal. The Fenton process destroyed MPPs, releasing small molecules and increasing the dissolved organic carbon by 20%. The fragmented MPPs adsorbed Fe3+, SAs, and intermediates of SAs. Fragmentation and polar groups significantly increased, resulting in new hazards after the Fenton process treatment. MPPs increased the difficulty of SAs removal, making the treated solution and MPPs potentially hazardous.

Typical Sulfonamide Antibiotics Removal by Biochar-Amended River Coarse Sand during Groundwater Recharge.

The high porosity of medium-coarse sand (MCS) layers in groundwater recharge areas presents a high environmental risk. Sulfamethoxazole (SMX) and trimethoprim (TMP) are two common sulfonamide antibiotics in surface water that have a high propensity to migrate into groundwater. In this study, four biochars were prepared and biochar-amended soil aquifer treatment (SAT) columns were constructed to remove SMX and TMP. Batch experiments demonstrated that the sorption isotherms conformed to the Freundlich model. The maximum adsorptions of biochars prepared at 700 °C were 54.73 and 67.62 mg/g for SMX and 59.3 and 73.38 mg/g for TMP. Electrostatic interaction may be one of the primary mechanisms of adsorption. The column experiments showed that the SMX and TMP removal rate of the biochar-amended SAT was as high as 96%, while that of the MCS SAT was less than 5%. The addition of biochar greatly improved the retention capacity of the pollutants in the MCS layer in the groundwater recharge area and effectively reduced environmental risk.

Selective photocatalytic removal of sulfonamide antibiotics: The performance differences in molecularly imprinted TiO2 synthesized using four template molecules

Four types of molecularly imprinted TiO2 photocatalysts named MIP-TiO2/sulfadiazine (SD), MIP-TiO2/sulfamethoxazole (SMX), MIP-TiO2/sulfonamide (SN) and MIP-TiO2/aniline (AN), were synthesized. The five catalysts exhibited different degrees of selectivity for two types of sulfonamide antibiotics (SAs), SD and SMX. In the systems of NIP–TiO2, MIP-TiO2/SD, MIP-TiO2/SMX, MIP-TiO2/SN and MIP-TiO2/AN, the degradation rate constants of SD were 0.0789, 0.1031, 0.0859, 0.1034 and 0.1051 min−1, respectively. Moreover, the removal rate constants of SMX on the mentioned catalysts were 0.1076, 0.3250, 0.4260, 0.3885 and 0.5848 min−1, correspondingly. The single bond cleavage (C–S, C–N, and S–N bonds), hydroxylation, ring-opening, oxidation, and deamination were the major transformation pathways of SAs. With the presence of MIP-TiO2/SN and MIP-TiO2/AN, more low molecular weight products were generated, and the intermediates preferred to go through further hydroxylation and oxidation reactions. Therefore, besides MIP-TiO2/SD and MIP-TiO2/SMX, the novel MIP-TiO2/SN and MIP-TiO2/AN, which were prepared by using substances with the similar main functional groups as SAs as template molecules, had excellent catalytic abilities and less byproducts formed in the situation. The results may provide an effective idea to level up the SAs degradation rates, control the generation of intermediates, and reduce environmental risks.

Enhanced removal of sulfonamide antibiotics from water by phosphogypsum modified biochar composite

Antibiotic pollution has become a global eco-environmental issue. To reduce sulfonamide antibiotics in water and improve resource utilization of solid wastes, phosphogypsum modified biochar composite (PMBC) was prepared via facile one-step from distillers grains, wood chips, and phosphogypsum. The physicochemical properties of PMBC were characterized by scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), Zeta potential, X-ray diffraction (XRD), etc. The influencing factors, adsorption behaviors, and mechanisms of sulfadiazine (SD) and sulfamethazine (SMT) onto PMBC were studied by batch and fixed bed column adsorption experiments. The results showed that the removal rates of SD and SMT increased with the increase of phosphogypsum proportion, while decreased with the increase of solution pH. The maximum adsorption capacities of modified distillers grain and wood chips biochars for SD were 2.98 and 4.18 mg/g, and for SMT were 4.40 and 8.91 mg/g, respectively, which was 9.0–22.3 times that of pristine biochar. Fixed bed column results demonstrated that PMBC had good adsorption capacities for SD and SMT. When the solution flow rate was 2.0 mL/min and the dosage of PMBC was 5.0 g, the removal rates of SD and SMT by modified wood chips biochar were both higher than 50% in 4 hr. The main mechanisms of SD and SMT removal by PMBC are hydrogen bonding, π-π donor-acceptor, electrostatic interaction, and hydrophobic interaction. This study provides an effective method for the removal of antibiotics in water and the resource utilization of phosphogypsum.

Construction of Ag nanocluster-modified Ag3PO4 containing silver vacancies via in-situ reduction: With enhancing the photocatalytic degradation activity of sulfamethoxazole

Photocatalytic removal of sulfonamide antibiotics is an effective strategy to solve environmental pollution. Ag3PO4 is a promising anode material for photocatalytic material with photocatalytic degradation ability under ultraviolet light or natural light. Unfortunately, due to its instability, Ag+ could be reduced to Ag0 which loaded onto the surface of Ag3PO4 during the photocatalytic process, causing self-photocorrosion and resulting in the reduction of photocatalytic activity and stability. Herein, Ag3PO4 nanoparticles loaded with Ag nanoclusters containing Ag vacancies (Ag/Ag3PO4-VAg) were constructed by an in-situ reduction strategy to achieve effectively photocatalytic degradation behavior. The Ag nanoclusters loaded on the surface of Ag3PO4 can not only effectively inhibit the self-photocorrosion but also affords a localized surface plasmon resonance (LSPR) effect in the photocatalytic process, thus leading to the efficient generation and rapid transfer of photogenerated carriers behavior. In addition, the Ag vacancies in Ag3PO4 are crucial to increasing the adsorption energy of H2O for further enhancing the capture and accumulation of electrons. In detail, according to Zeta potential analysis, the strong adsorption sites of sulfamethoxazole (SMX) molecules are generated at the interface of Ag and Ag3PO4, which promote the activation of SMX molecules. A 100 ml of 20 mg/L SMX could be completely degraded within 15 min with an apparent rate constant (Kapp) of 0.306 min−1, which far exceeds the activity of most of the photocatalysts. This work may provide an attractive strategy to address the activity, stability of Ag3PO4 and and realizing the green remediation of SMX wastewater.

Degradation of sulfonamides in aquaculture wastewater by laccase–syringaldehyde mediator system: Response surface optimization, degradation kinetics, and degradation pathway

As a new type of environmental pollutant, environmental antibiotic residues have attracted widespread attention, and the degradation and removal of antibiotics has become an engaging topic for scholars. In this paper, Novozym 51003 industrialized laccase and syringaldehyde were combined to degrade sulfonamides in aquaculture wastewater. Design Expert10 software was used for multiple regression analysis, and a response surface regression model was established to obtain the optimal degradation parameters. In the actual application, the degradation system could maintain a stable performance within 9 h, and timely supplement of the mediator could achieve a better continuous degradation effect. Low concentrations of heavy metals and organic matter would not significantly affect the degradation performance of the laccase–mediator system, making the degradation system suitable for a wide range of water quality. Enzymatic reaction kinetics demonstrated a strong affinity of sulfadiazine to the substrate. Ten degradation products were speculated using high-resolution mass spectrum based on the mass/charge ratios and the publication results. Four types of possible degradation pathways of sulfadiazine were deduced. This work provides a practical method for the degradation and removal of sulfonamide antibiotics in actual sewage.

Quantifying the contribution rates of sulfonamide antibiotics removal mechanisms in constructed wetlands using multivariate statistical analysis

The removal of antibiotics in subsurface flow constructed wetlands is performed through various removal mechanisms, such as adsorption, hydrolysis, microbial degradation and plant uptake. However, the contribution rates of the removal mechanisms in constructed wetlands are still not well studied. This study conducted a series of experiments and used multivariate statistical analysis to determine contribution rates for substrate adsorption, hydrolysis, and microbial degradation. Multiple stepwise regression analysis indicated that specific surface area and salt content were the main factors influencing sulfonamide adsorption, while temperature and pH were the main factors influencing sulfonamide hydrolysis. Variance partitioning analysis showed that the influence of physical-chemical factors was greater than that of nutrients on the microbial community. Partial least squares path analysis showed that the path coefficients of microbial degradation, adsorption and hydrolysis for sulfonamides removal in vertical subsurface flow constructed wetlands were 0.6339, 0.3608 and 0.0351, respectively, while the corresponding path coefficient were 0.5658, 0.4707 and 0.1079 in horizontal subsurface flow constructed wetlands, respectively. This means that microbial degradation contributes the most to the removal of sulfonamides in subsurface flow constructed wetlands. Enhanced microbial degradation may be a powerful measure to improve the removal of sulfonamides. These results will be helpful for understanding the removal mechanism of antibiotics and will provide a definite direction for pertinently improving sulfonamide removal efficiency in constructed wetlands.