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Sulfonamides (SAs) in agricultural soils can be degraded in rhizosphere, but can also be taken up by vegetables, which thereby poses human health and ecological risks. A glasshouse experiment was conducted using multi-interlayer rhizoboxes to investigate the fate of three SAs in rape and hot pepper rhizosphere soil systems to examine the relationship between the accumulation and their physicochemical processes. SAs mainly entered pepper shoots in which the accumulation ranged from 0.40 to 30.64 mg kg-1, while SAs were found at high levels in rape roots ranged from 3.01 to 16.62 mg kg-1. The BCFpepper shoot exhibited a strong positive linear relationship with log Dow, while such relationship was not observed between other bioconcentration factors (BCFs) and log Dow. Other than lipophilicity, the dissociation of SAs may also influence the uptake and translocation process. Larger TF and positive correlation with log Dow indicate preferential translocation of pepper SAs. There was a significant (p < 0.05) dissipation gradient of SAs observed away from the vegetable roots. In addition, pepper could uptake more SAs under solo exposure, while rape accumulated more SAs under combined exposure. When SAs applied in mixture, competition between SAs might occur to influence the translocation and dissipation patterns of SAs.

The phloem and xylem structure of plants and the neutral and ionic partitioning of sulfonamides (SAs) influence the uptake and translocation of SAs.A significant (p < 0.05) dissipation gradient of SAs was observed away from the vegetable roots.Combined exposure could promote the correlation between log BCF and log D_ow.

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The environmental and health risks associated with sulfonamide antibiotics (SAs) are receiving increasing attention. Through multi-spectroscopy, density functional theory (DFT), and molecular docking, this study investigated the interaction features and mechanisms between six representative SAs and human serum albumin (HSA). Multi-spectroscopy analysis showed that the six SAs had significant binding capabilities with HSA. The order of binding constants at 298 K was as follows: sulfadoxine (SDX): 7.18 × 105 L mol-1 > sulfamethizole (SMT): 6.28 × 105 L mol-1 > sulfamerazine (SMR): 2.70 × 104 L mol-1 > sulfamonomethoxine (SMM): 2.54 × 104 L mol-1 > sulfamethazine (SMZ): 3.06 × 104 L mol-1 > sulfadimethoxine (SDM): 2.50 × 104 L mol-1. During the molecular docking process of the six SAs with HSA, the binding affinity range is from -7.4 kcal mol-1 to -8.6 kcal mol-1. Notably, the docking result of HSA-SDX reached the maximum of -8.6 kcal mol-1, indicating that SDX may possess the highest binding capacity to HSA. HSA-SDX binding, identified as a static quenching and exothermic process, is primarily driven by hydrogen bonds (H bonds) or van der Waals (vdW) interactions. The quenching processes of SMR/SMZ/SMM/SDX/SMT to HSA are a combination of dynamic and static quenching, indicating an endothermic reaction. Hydrophobic interactions are primarily accountable for SMR/SMZ/SMM/SDX/SMT and HSA binding. Competition binding results revealed that the primary HSA-SAs binding sites are in the subdomain IB of the HAS structure, consistent with the results of molecule docking. The correlation analysis based on DFT calculations revealed an inherent relationship between the structural chemical features of SAs and the binding performance of HSA-SAs. The dual descriptor (DD) and the electrophilic Fukui function were found to have a significant relationship (0.71 and -0.71, respectively) with the binding constants of HSA-SAs, predicting the binding performance of SAs and HSA. These insights have substantial scientific value for evaluating the environmental risks of SAs as well as understanding their impact on biological life activities.

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To solve the problems of unstable adsorption performance and high organic solvent consumption of traditional molecular imprinting materials, we developed a water-resistant and highly adsorptive molecularly imprinted sulfamethazine polymer (MIP) through a novel synthetic strategy consisting of the application of mixed functional monomers combined with hydrophobic crosslinkers. The results showed that the imprinting factor of the prepared MIP was increased from 0.93 to 4.38, and that the relative selection coefficient k' was 5.59. With the application of the material to be developed as a solid-phase extraction (SPE) filler for sulfonamides (SAs) in milk combined with UPLC-MS/MS, the validated method showed a sensitive quantification limit (0.89 µg/kg), a steady recovery (95.55%-97.97%) and an excellent precision (0.08%-2.92% RSD). Moreover, after 5 times usage, the recovery rate of MIP-SPE was still above 90%. Therefore, the prepared materials showed high performance of molecular adsorption and were water-resistant, which was also considered an excellent filler of SPE for SAs extraction in food or other fields.

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Effective degradation of sulfonamides (SAs) in water is of global importance for decreasing its pathogenicity and bioaccumulation. In this study, Mn3(PO4)2 was used as a carrier to fabricate a novel and high-efficient catalyst with Co3O4 anchored (Co3O4@Mn3(PO4)2) for the activation of peroxymonosulfate (PMS) to degrade SAs. Surprisingly, the catalyst exhibited superior performance, and nearly 100% of SAs (10 mg L-1) including sulfamethazine (SMZ), sulfadimethoxine (SDM), sulfamethoxazole (SMX), and sulfisoxazole (SIZ) was degraded by Co3O4@Mn3(PO4)2-activated PMS within 10 min. A series of characterization of the Co3O4@Mn3(PO4)2 composite were conducted and the main operational parameters of SMZ degradation were investigated. SO4•-, •OH, and 1O2 were determined to be the dominating reactive oxygen species (ROS) responsible for the degradation of SMZ. Co3O4@Mn3(PO4)2 also exhibited excellent stability and the removal rate of SMZ still maintained over 99% even in the fifth cycle. The plausible pathways and mechanisms of SMZ degradation in the system of Co3O4@Mn3(PO4)2/PMS were deduced on the basis of the analyses of LCMS/MS and XPS. This is the first report on high-efficient heterogeneous activating PMS by mooring Co3O4 on Mn3(PO4)2 to degrade SAs, which provides us with a strategy to structure novel bimetallic catalysts for PMS activation.

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Habitats of species and physicochemical factors are of great importance in determining the trophic transfer of contaminants in freshwater ecosystems. There is little information on how multiple physicochemical factors and habitats influence the trophic transfer of antibiotics in freshwater food webs. This study investigated the concentrations of 7 sulfonamides (SAs), 4 fluoroquinolones (FQs), 4 tetracyclines (TCs) and 2 macrolides (MLs) in the Lake Dianshan food web. Stable isotope analysis (SIA), and mathematical models were used to assign trophic levels and distinguish between the benthic food web (BFW) and pelagic food web (PFW). Values of stable nitrogen isotope (δ15N‰) and stable carbon isotope (δ13C‰) ranged from 10.2 ± 0.11 to 19.72 ± 0.05 and -33.67 ± 0.18 to -20.79 ± 0.50, respectively. Total concentrations of antibiotics ranged from 36.63 ± 12.73 ng/g dry weight (dw) to 105.85 ± 12.95 ng/g dw for all species. The relative abundance of antibiotics was in the following order: ∑FQs (36.49 %) > ∑SAs (26.70 %), >∑MLs (12.63 %) for all biotas. Trophic magnification factor (TMFs) values for individual antibiotics ranged from 0.10 to 1.20 and 0.31 to 1.82 for PFW and BFW, respectively. Three classes of antibiotics ∑FQs (p < 0.05), ∑TCs (p < 0.05), and ∑MLs (p < 0.05) showed significant trophic dilution in PFW, opposite to non-significant trophic dilution in BFW. The influence of various physicochemical factors was not strong over trophic transfer (e.g., octanol-water partition coefficient-LogKow (r = -0.05 in PFW, r = -0.14 in BFW) and distribution coefficient-LogD (r = 0.06 in PWF, r = -0.28 in BFW)) except for aqueous solubility (LogS). Results indicated a significantly higher trophic dilution of antibiotics in the PFW than in the BFW. Among the studied six physicochemical factors, only LogS significantly influences (p < 0.05) the trophic transfer of antibiotics in the freshwater food web. Health risk assessments indicated that currently, there were no serious risks present for urban and rural populations.

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With polyacrylonitrile nanofibers mat (PAN NFsM) as a template, molecularly imprinted resin/polydopamine nanofibers mat (MIR/PDA NFsM) was synthesized for the extraction of sulfonamides (SAs) in water. The specific surface area and pore volume were increased obviously due to the functionalization of MIR. The adsorption efficiencies of MIR/PDA NFsM under optimized conditions for SAs were 92.3-99.3%. Possible adsorption mechanisms of imprinting recognition and hydrogen bond interactions were also put forward. Compared with MIR particles, the MIR/PDA NFsM exhibited much superior adsorption performance. Particularly, the outstanding mass transfer efficiency of MIR/PDA NFsM was much higher than the other reported adsorbents for SAs. Finally, a new method based on the solid-phase extraction (SPE) of MIR/PDA NFsM was successfully developed for the detection of five SAs in environmental water with HPLC-MS/MS and applied to the analysis of actual samples. Under the selected conditions, the enrichment factors of MIR/PDA NFsM of SCP, SMT, SMZ, SMR, and SMX were between 23.0 and 25.0. Low detection limits (0.26-0.76 ng L-1), broad linear range (1.0 ng L-1 to 10.0 µg L-1), and satisfactory recoveries (82.8-115.6%) and precisions (RSDs < 7.2%) were obtained. Moreover, the excellent reusability properties and storage stability endowed MIR/PDA NFsM with great value for practical applications.

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Using MIL-101(Fe) as the source of carbon and Fe, a magnetic porous carbon (MPC) material with Fe3C nanoparticles encapsulated in porous carbon was prepared through one-pot pyrolysis under N2 atmosphere. With MPC as adsorption material, a stir bar sorptive-dispersive microextraction (SBSDME) method was proposed to extract and preconcentrate sulfonamides (SAs) prior to HPLC-DAD determination. To investigate their extraction ability, different MPC materials were prepared under different carbonization temperatures (600, 700, 800, 900, and 1000 °C). The material prepared under 900 °C (MPC-900) exhibited the highest extraction ability for SAs. The as-prepared MPC materials were also characterized by Raman spectroscopy, scanning electron microscopy, X-ray photoelectron spectroscopy, zeta potential, and other techniques. The main parameters that affect extraction were systematically studied. Under optimal conditions, favorable linearity (R2 ≥ 0.9938) and detection limits (0.02-0.04 ng mL-1) of sulfonamides were obtained. The average recoveries for spiked milk and lake water samples ranged from 76.9 to 109% and from 75.4 to 118% with RSDs of 3.10-9.63% and 1.71-11.3%, respectively. Sulfameter and sulfisoxazole were detected in milk sample. Sulfisoxazole was detected in the lake water sample. The MPC-900 material demonstrated excellent reusability. It can be reused 24 times with peak areas having no obvious decline. The method can be applied to extract ultra-trace compounds in complex sample matrices. Schematic presentation of a stir bar sorptive-dispersive microextraction (SBSDME) by using magnetic porous carbon (MPC) composites as sorbent combined with high-performance liquid chromatography for sensitive analysis of sulfonamides in milk and lake water samples.

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Sulfonamides (SAs) and sul antibiotic resistance genes (ARGs) have been extensively detected in drinking water sources and warrant further studies on the removal of them in different drinking water treatment processes (DWTPs). The prevalence of 13 SAs, sul1, sul2 and class I integrase gene intI1 in conventional and advanced processes was investigated using HPLC-MS/MS and real-time quantitative PCR (qPCR), respectively. The most abundant SA was sulfamethoxazole, with the maximum concentration of 67.27 ng/L. High concentration of sulfamethoxazole was also measured in finished water in both conventional (22.05 ng/L) and advanced (11.24 ng/L) processes. Overall, the removal efficiency of advanced process for each SA was higher than that of conventional process, except for sulfameter. The absolute concentrations of sul1, sul2 and intI1 in raw water ranged from 1.8 × 103 to 2.4 × 105 gene abundance/mL. After treatment, the residual sul ARGs and intI1 in finished water still remained at 102 - 104 gene abundance/mL. Conventional treatment units, including flocculation/sedimentation/sand filtration, played a more important role in removing sul1, sul2 and intI1 than oxidation (chlorination or ozonation) and granular activated carbon filtration treatments. Based on this work, more investigations are needed to help improve the removal of both antibiotics and ARGs in DWTPs.

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Using magnetic silica (Fe2O3@SiO2) as the matrix material, a magnetic reversed-phase restricted access material was prepared via surface-initiation atom transfer radical polymerization (SI-ATRP) on the surface of modified Fe2O3@SiO2. Stearyl methacrylate (SMA) was grafted on the inner surface of the modified Fe2O3@SiO2, and glycidylmethacrylate (GMA) was grafted on the outer surface of the modified Fe2O3@SiO2. The magnetic reversed-phase restricted access material was prepared via acid hydrolysis. This material was characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM) and elemental analysis. The exclusion ability of the opened magnetic reversed-phase restricted access material to bovine serum albumin (BSA) was 90.4%. The maximum adsorbed amounts of sulfisoxazole (SIZ), sulfadimethoxine (SDM), trimethoprim (TMP) and sulfamerazine (SMR) were 2.76, 2.24, 1.51 and 1.34 mg/g, respectively. This material was applied to extract and enrich SIZ, SMR and SDM in milk and bovine serum samples. The spiked recoveries of SIZ, SMR and SDM were 88.7%-90.8%, and the relative standard deviations were 3.3%-5.3%. Thus, the magnetic phase restricted access material can simplify the pretreatment of biological matrix samples, and can be applied to the analysis and detection of blood samples or food samples.

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A magnetic, mesoporous core/shell structured Fe3O4@JUC-48 nanocomposite was synthesized and employed as a magnetic solid phase extraction (MSPE) sorbent for the determination of trace sulfonamides (SAs) in meat samples. The synthesized nanocomposite was characterized by X-ray diffraction, Fourier transform infrared spectra, transmission electron microscopy, scanning electron microscopy, Brunner-Emmet-Teller, and vibrating sample magnetometry; the Fe3O4@JUC-48 nanocomposite exhibited a distinctive morphology, large surface area, high magnetism, open adsorption sites, and high chemical stability. By combining the optimized MSPE conditions with high performance liquid chromatography diode array detection, an accurate and sensitive method for the determination of 5 SAs, including sulfadiazine (SDZ), sulfathiazole (STZ), sulfamerazine (SMR), sulfamethazine (SMZ), and sulfamethoxypyridazine (SMP), was developed. The method exhibited good linearity in the range of 3.97-1000ng/g with R ranging from 0.9991 to 0.9994, high sensitivity with LODs ranging from 1.73 to 5.23ng/g, adequate recoveries between 76.1 and 102.6% with low relative standard deviations ranging from 2.1 to 6.4%, and high precision with RSD<4.5%. The Fe3O4@JUC-48 magnetic nanocomposite is a promising sorbent for the rapid and efficient extraction of SAs from complex biological samples such as chicken, pork, and shrimp.

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