Magnetic COFs for the adsorptive removal of diclofenac and sulfamethazine from aqueous solution: Adsorption kinetics, isotherms study and DFT calculation.

Covalent organic frameworks (COFs) are emerging and promising adsorbents for the adsorptive removal of many types of pollutants. However, most COFs fabricated by various methods are in the form of microcrystalline powders, making them difficult in separation. In this study, magnetic COFs were prepared by a simple impregnation method. The as-prepared samples with Ms = 5.2 emu g-1 showed a good magnetic separation capability. Additionally, the adsorption performance of magnetic COFs towards antibiotics (e.g., diclofenac and sulfamethazine) was also studied. Various adsorption kinetic models (e.g., the pseudo first-order, the pseudo second-order, and mixed-order models) and adsorption isotherm models (e.g., the Freundlich, the Langmuir, and the Sips models) were used to study their adsorption kinetics and isotherms. Furthermore, density functional theory (DFT) was utilized to predict the interaction between adsorbents and adsorbates and to explain the partial adsorption mechanisms.

Multiresidue Determination of 27 Sulfonamides in Poultry Feathers and Its Application to a Sulfamethazine Pharmacokinetics Study on Laying Hen Feathers and Sulfonamide Residue Monitoring on Poultry Feathers.

A method for the simultaneous determination of 27 sulfonamides in poultry feathers using ultra performance liquid chromatography-tandem mass spectrometry (UPLC-MS/MS) was established in this study. The samples were extracted using 0.1 mol/L HCl solutions in a 60 °C water bath for 2 h, purified using hydrophilic-lipophilic balance solid-phase extraction, nitrogen-dried, and then reconstituted for UPLC-MS/MS analysis, which was performed with a CSH-C18 column. Linearity, limit of detection, limit of quantification, recovery, and precision were calculated in accordance with Commission Decision 2002/657/EC. For linearity, all standard curves showed a standard coefficient greater than 0.99, and the recoveries and coefficient of variation were 89-115% and <20%, respectively. The limit of detection and limit of quantification were 0.2-5 and 0.5-20 ng/g, respectively. The method was successfully applied to sulfamethazine (SMZ) residue accumulation monitoring in laying hen feathers and sulfonamide residue monitoring on poultry feathers. SMZ residue accumulation in the laying hen feathers was studied after administration with 100 mg/kg of SMZ for 21 consecutive days. SMZ residues were still detected in feathers 14 days after drug administration and persisted for up to 85 days. Results from 42 poultry feather samples showed that the feather is a suitable medium to monitor the illegal use of sulfonamides in poultry production.

Electrochemical immunosensor based on Ag+-dependent CTAB-AuNPs for ultrasensitive detection of sulfamethazine.

An electrochemical biosensor was proposed utilizing an improved amplification strategy for the rapid detection of sulfamethazine (as a model target) in aquatic environments. In this competitive immunoassay, cetyltrimethylammonium bromide-capped gold nanoparticles (CTAB-AuNPs) were used as a signal amplifier and electrode matrix and coated with an antigen-antibody (Cag-Ab1) specific binding system as a recognition unit for the target compound. In addition, silver nanoparticle labels were functionalized with dendritic fibrous nanosilica (DFNS@AgNPs) and decorated onto chitosan/single walled carbon nanohorn (CS/SWCNH)-modified glass carbon electrodes (GCEs), which improved the electron transfer rate and increased the surface area, enabling more coating antigens to be captured. Under acidic conditions, massive amounts of the Ag+ bound to the surface of the AuNPs dissolved, and consequently, formed Ag+@CTAB-AuNP complexes, which resulted in a distinctly improved peroxidase-like activity and enhanced current response. Furthermore, the destroyed Ab1-Ab2-DFNS conjugation greatly decreased the impedance, bringing about the amplification of the electrochemical signals. After optimization of the parameters, the proposed approach exhibited excellent performance, including good sensitivity (LOD, 0.0655 ng/mL) and satisfactory accuracy (recoveries, 79.02%-118.39%; CV, 3.18%-9.82%), which indicates the great potential of this strategy for the rapid detection of trace pollutants in the environments.

Removal of Sulfamethoxazole, Sulfathiazole and Sulfamethazine in their Mixed Solution by UV/H2O2 Process.

Sulfamethoxazole (SMZ), sulfathiazole (STZ) and sulfamethazine (SMT) are typical sulfonamides, which are widespread in aqueous environments and have aroused great concern in recent years. In this study, the photochemical oxidation of SMZ, STZ and SMT in their mixed solution using UV/H2O2 process was innovatively investigated. The result showed that the sulfonamides could be completely decomposed in the UV/H2O2 system, and each contaminant in the co-existence system fitted the pseudo-first-order kinetic model. The removal of sulfonamides was influenced by the initial concentration of the mixed solution, the intensity of UV light irradiation, the dosage of H2O2 and the initial pH of the solution. The increase of UV light intensity and H2O2 dosage substantially enhanced the decomposition efficiency, while a higher initial concentration of mixed solution heavily suppressed the decomposition rate. The decomposition of SMZ and SMT during the UV/H2O2 process was favorable under neutral and acidic conditions. Moreover, the generated intermediates of SMZ, STZ and SMT during the UV/H2O2 process were identified in depth, and a corresponding degradation pathway was proposed.

Rapid Detection of the Antibiotic Sulfamethazine in Pig Body Fluids by Paper Spray Mass Spectrometry.

We report herein a practical method for nonlethal detection of the antibiotic sulfamethazine in pig body fluids via the combination of simple extraction and paper spray mass spectrometry (PS-MS). This method requires minimal sample preparation while still providing high sensitivities and accuracies in complex matrices including pig whole blood (LOD = 7.9 µg/L; recovery = 95.4-103.7%), pig serum (LOD = 11.5 µg/L; recovery = 103.2-106.2%), and synthetic urine (LOD = 11.2 µg/L; recovery = 99.1-103.2%). Given a known correlation between the level of sulfamethazine in body fluids and edible tissues, this method shows great promise as a practical and nonlethal solution for rapid testing of the drug, which can substantially aid managerial decision in the livestock industry.

Removal mechanism of sulfamethazine and its intermediates from water by a rotating advanced oxidation contactor equipped with TiO2-high-silica zeolite composite sheets.

The removal of antibiotic sulfamethazine (SMT) and its intermediates from water was investigated using a rotating advanced oxidation contactor (RAOC) equipped with TiO2-high-silica zeolite composite sheets. SMT was readily removed from water through adsorption onto high-silica zeolite and photocatalytic decomposition by TiO2 inside the composite sheet. Some degradation intermediates were retained and photocatalytically decomposed inside the composite sheet. Relatively hydrophobic intermediates such as hydroxylated SMT were captured inside the sheets, whereas hydrophilic intermediates were distributed in water. This was attributed to the hydrophobic interactions in the adsorption mechanism of high-silica zeolite. The time courses of the NH4+, NO3-, and SO42- ion concentration during the RAOC treatment of SMT were evaluated. After treatment by RAOC for 24 h, approximately 94% of nitrogen derived from the amino and sulfanilamide groups and 39% of sulfur from the sulfanilamide group were mineralized, which indicated that the mineralization behavior of SMT treated by RAOC was different from that treated by TiO2 powder. These results strongly suggested that the dissociation of the amino group and cleavage of the sulfonamide group and subsequent dissociation of the amino group preferentially proceeded inside the composite sheets.

Sorptive removal of ionizable antibiotic sulfamethazine from aqueous solution by graphene oxide-coated biochar nanocomposites: Influencing factors and mechanism.

Significant concerns have been raised over antibiotics pollution in aquatic environments in recent years. In this study, sorption of sulfamethazine (SMT) by novel graphene oxide-coated biochar nanocomposites (GO-BC) based on graphene oxide (GO) with bamboo sawdust biochar (BC) was investigated. In comparison with the original BC, the sorption capacity of GO-BC for SMT increased by 1.14 times. Sorption of SMT onto GO-BC was proved to be dominantly by chemisorption, and Freundlich isotherm described the sorption adequately. It was found that variation of pH and ionic strength obviously affected the sorption of SMT, and GO-BC had a good sorption effect on SMT at pH 3.0-6.0 and lower ionic strength. Obvious enhancement (by 30%) in sorption of SMT on GO-BC was observed, which might be attributed to the increase of functional groups on the surface of GO-BC. Moreover, the main sorption mechanism for SMT was π-π electron-donor-acceptor interaction, while auxiliary sorption mechanisms were inferred as pore-filling, cation exchange, hydrogen bonding interaction and electrostatic interaction. The results indicated that GO-BC sorption was an efficient way for the removal of SMT.

Removal of sulfamethazine antibiotics using CeFe-graphene nanocomposite as catalyst by Fenton-like process.

The presence of sulfonamide (SMT) antibiotics in aquatic environments has received increasing attention in recent years, and they are ubiquitous pollutants which cannot be effectively removed by conventional wastewater treatment processes. In this paper, the nanocomposites Ce(0)/Fe(0)-reduced graphene oxide (Ce(0)/Fe(0)-RGO) were synthesized through chemical reduction method, and characterized by Raman and FTIR before and after use. The addition of RGO can prevent the agglomeration of Ce(0) and Fe(0). The elimination of SMT can be divided into adsorption and degradation process. The adsorption of SMT onto the catalyst can enhance its degradation. The effect of pH value, concentration of H2O2, catalyst dosage, temperature and initial SMT concentration on the removal efficiency of SMT was determined. When pH = 7, T = 25 °C, H2O2 = 8 mM, Ce(0)/Fe(0)-RGO = 0.5 g/L, SMT = 20 mg/L, the removal efficiency of SMT and TOC was 99% and 73%, respectively. The stability of the catalysts was evaluated with repeated batch experiments using ethanol, water and acid as solvents to wash the used catalysts, respectively. The surface change of the catalysts after each use was characterized by Raman and FTIR analysis. The intermediates were detected by GC-MS and IC, the possible degradation pathway of SMT was tentatively proposed.

Synchronized separation, concentration and determination of trace sulfadiazine and sulfamethazine in food and environment by using polyoxyethylene lauryl ether-salt aqueous two-phase system coupled to high-performance liquid chromatography.

Polyoxyethylene lauryl ether (POELE10)-Na2C4H4O6 aqueous two-phase extraction system (ATPES) is a novel and green pretreatment technique to trace samples. ATPES coupled with high-performance liquid chromatography (HPLC) is used to analyze synchronously sulfadiazine (SDZ) and sulfamethazine (SMT) in animal by-products (i.e., egg and milk) and environmental water sample. It was found that the extraction efficiency (E%) and the enrichment factor (F) of SDZ and SMT were influenced by the types of salts, the concentration of salt, the concentration of POELE10 and the temperature. The orthogonal experimental design (OED) was adopted in the multi-factor experiment to determine the optimized conditions. The final optimal condition was as following: the concentration of POELE10 is 0.027gmL(-1), the concentration of Na2C4H4O6 is 0.180gmL(-1) and the temperature is 35°C. This POELE10-Na2C4H4O6 ATPS was applied to separate and enrich SDZ and SMT in real samples (i.e., water, egg and milk) under the optimal conditions, and it was found that the recovery of SDZ and SMT was 96.20-99.52% with RSD of 0.35-3.41%. The limit of detection (LOD) of this method for the SDZ and SMT in spiked samples was 2.52-3.64pgmL(-1), and the limit of quantitation (LOQ) of this method for the SDZ and SMT in spiked samples was 8.41-12.15pgmL(-1).

Facile synthesis of magnetic hypercrosslinked polystyrene and its application in the magnetic solid-phase extraction of sulfonamides from water and milk samples before their HPLC determination.

In this study, a novel magnetic solid-phase extraction (MSPE) sorbent, magnetic hypercrosslinked polystyrene (HCP/Fe3O4), was prepared and used for preconcentration of four sulfonamides (sulfamethoxypyridazine, sulfamethazine, sulfamethoxazole and sulfachloropyridazine) from natural water and milk samples. This material was prepared by sorption of pre-synthesized Fe3O4 nanoparticles (NPs) onto HCP. A number of sorbents with varying Fe3O4NPs content were prepared, and their structural, magnetic and sorption properties were studied. Various experimental parameters affecting the extraction efficiencies such as the amount of the magnetic nanocomposite, extraction time, pH of the sample solution and desorption conditions were studied and optimized. Under the optimal conditions, a convenient and efficient method for the determination of sulfonamides in water and milk samples was developed by combining MSPE and high-performance liquid chromatography with amperometric detection. The results showed that the recoveries of these compounds were in the range of 84-105% with the relative standard deviations ranging between 3% and 10%; the limit of detection were in the range of 0.21-0.33 ng mL(-1) for water and 2.0-2.5 ng mL(-1) for milk.

Elimination patterns of worldwide used sulfonamides and tetracyclines during anaerobic fermentation.

Antibiotics such as sulfonamides and tetracyclines are frequently used in veterinary medicine. Due to incomplete absorption in the animal gut and/or unmetabolized excretion, the substances can enter the environment by using manure as soil fertilizer. The anaerobic fermentation process of biogas plants is discussed as potential sink for antibiotic compounds. However, negative impacts of antibiotics on the fermentation process are suspected. The elimination of sulfadiazine, sulfamethazine, tetracycline and chlortetracycline in semi-continuous lab-scale fermenters was investigated. Both biogas production and methane yield were not negatively affected by concentrations up to 38 mg per kg for sulfonamides and 7 mg per kg for tetracyclines. All substances were partly eliminated with elimination rates between 14% and 89%. Both matrix and structure of the target molecule influenced the elimination rate. Chlortetracycline was mainly transformed into iso-chlortetracycline. In all other cases, the elimination pathways remained undiscovered; however, sorption processes seem to have a negligible impact.

Enhanced sulfamethazine removal by steam-activated invasive plant-derived biochar.

Recent investigations have shown frequent detection of pharmaceuticals in soils and waters posing potential risks to human and ecological health. Here, we report the enhanced removal of sulfamethazine (SMT) from water by physically activated biochar. Specifically, we investigated the effects of steam-activated biochars synthesized from an invasive plant (Sicyos angulatus L.) on the sorption of SMT in water. The properties and sorption capacities of steam-activated biochars were compared with those of conventional non-activated slow pyrolyzed biochars. Sorption exhibited pronounced pH dependence, which was consistent with SMT speciation and biochar charge properties. A linear relationship was observed between sorption parameters and biochar properties such as molar elemental ratios, surface area, and pore volumes. The isotherms data were well described by the Freundlich and Temkin models suggesting favorable chemisorption processes and electrostatic interactions between SMT and biochar. The steam-activated biochar produced at 700 °C showed the highest sorption capacity (37.7 mg g(-1)) at pH 3, with a 55% increase in sorption capacity compared to that of non-activated biochar produced at the same temperature. Therefore, steam activation could potentially enhance the sorption capacities of biochars compared to conventional pyrolysis.

Rapid and sensitive immunochromatographic strip for on-site detection of sulfamethazine in meats and eggs.

A rapid immunochromatographic (ICG) strip based on a conjugate of colloidal gold and monoclonal antibody (mAb) was developed for the rapid, sensitive, and on-site detection of sulfamethazine in meat and egg samples. The detection limit of the ICG strip is 2 ng/mL, and the assay can be completed in 10 min. A cross-reactivity test indicated that the ICG strip was highly specific to sulfamethazine with no cross-reaction with sulfonamide compounds and other antibiotics. The results of the recovery test from meat and egg samples spiked with sulfamethazine were in good agreement with those obtained by the indirect competitive enzyme-linked immunosorbent assay. These results demonstrated that the ICG strip can be used as a rapid and qualitative tool for on-site screening of sulfamethazine in meat and egg samples.

Roles of extracellular polymeric substances (EPS) in the migration and removal of sulfamethazine in activated sludge system.

The occurrences, transformation of antibiotics in biological wastewater treatment plants have attracted increasing interests. However, roles of extracellular polymeric substances (EPS) of activated sludge on the fate of antibiotics are not clear. In this study, the roles of EPS in the migration and removal of one typical antibiotic, sulfamethazine (SMZ), in activated sludge process were investigated. The interaction between EPS and SMZ was explored through a combined use of fluorescence spectral analysis, laser light scattering and microcalorimetry techniques. Results show that SMZ interacted with the proteins in EPS mainly with a binding constant of 1.91 × 10(5) L/mol. The binding process proceeded spontaneously, and the driving force was mainly from the hydrophobic interaction. After binding, the structure of EPS was expanded and became loose, which favored the mass transfer and pollution capture. The removal of SMZ was influenced by interaction with EPS. SMZ could be effectively adsorbed on EPS, which accounted for up to 61.8% of total SMZ adsorbed by sludge at the initial adsorption stage and declined to around 35.3% at the subsequent biodegradation stage. The enrichment of SMZ by EPS was beneficial for SMZ removal and acquisition by microbes at the subsequent biodegradation stage.

MCM-48 modified magnetic mesoporous nanocomposite as an attractive adsorbent for the removal of sulfamethazine from water.

A novel magnetic mesoporous nanocomposite FeM48 was synthesized and applied to remove sulfamethazine (SMN) from water. The adsorption kinetics could be expressed by the pseudo-second-order model, where external and interfacial diffusions tended to be the rate-limiting step. The adsorption isotherms at varied temperatures were fitted well with Freundlich model, and thermodynamic analysis revealed that SMN adsorption on FeM48 was a spontaneous exothermic process. Solution pH exhibited a remarkable impact on the adsorption process and the maximum adsorbed concentration was obtained at pH 6.3. The effect of co-existing anions and humic acid demonstrated that SMN could be adsorbed selectively by FeM48. Hydrogen bonding between the nitrogen of the aniline, sulfinol or pyrimidine group of SMN and the surface hydroxyl group of FeM48 was the major driving force for adsorption. In addition, the π-π electron-donor-acceptor interaction between SMN (π-electron-acceptor) and MCM-48 (π-electron-donor) also promoted the adsorption process.

Control of the coordination status of the open metal sites in metal-organic frameworks for high performance separation of polar compounds.

Metal-organic frameworks (MOFs) with open metal sites have great potential for enhancing adsorption separation of the molecules with different polarities. However, the elution and separation of polar compounds on such MOFs packed columns using nonpolar solvents is difficult due to too strong interaction between polar compounds and the open metal sites. Here, we report the control of the coordination status of the open metal sites in MOFs by adjusting the content of methanol (MeOH) in the mobile phase for fast and high-resolution separation of polar compounds. To this end, high-performance liquid chromatographic separation of nitroaniline, aminophenol and naphthol isomers, sulfadimidine, and sulfanilamide on the column packed with MIL-101(Cr) possessing open metal sites was performed. The interaction between the open metal sites of MIL-101(Cr) and the polar analytes was adjusted by adding an appropriate amount of MeOH to the mobile phase to achieve the effective separation of the polar analytes due to the competition of MeOH with the analytes for the open metal sites. Fourier transform infrared spectra and X-ray photoelectron spectra confirmed the interaction between MeOH and the open metal sites of MIL-101(Cr). Thermodynamic parameters were measured to evaluate the effect of the content of MeOH in the mobile phase on the separation of polar analytes on MIL-101(Cr) packed column. This approach provides reproducible and high performance separation of polar compounds on the open metal sites-containing MOFs.

Biodegradation of sulfamethazine by Trametes versicolor: Removal from sewage sludge and identification of intermediate products by UPLC-QqTOF-MS.

Degradation of the sulfonamide sulfamethazine (SMZ) by the white-rot fungus Trametes versicolor was assessed. Elimination was achieved to nearly undetectable levels after 20 h in liquid medium when SMZ was added at 9 mg L(-1). Experiments with purified laccase and laccase-mediators resulted in almost complete removal. On the other hand, inhibition of SMZ degradation was observed when piperonilbutoxide, a cytochrome P450-inhibitor, was added to the fungal cultures. UPLC-QqTOF-MS analysis allowed the identification and confirmation of 4 different SMZ degradation intermediates produced by fungal cultures or purified laccase: desulfo-SMZ, N4-formyl-SMZ, N4-hydroxy-SMZ and desamino-SMZ; nonetheless SMZ mineralization was not demonstrated with the isotopically labeled sulfamethazine-phenyl-13C6 after 7 days. Inoculation of T. versicolor to sterilized sewage sludge in solid-phase systems showed complete elimination of SMZ and also of other sulfonamides (sulfapyridine, sulfathiazole) at real environmental concentrations, making this fungus an interesting candidate for further remediation research.

Development of a sensitive monoclonal antibody-based ELISA for the detection of sulfamethazine in cow milk, honey, and swine urine.

A specific monoclonal antibody (MAb) against sulfamethazine was produced with hybridoma technology. This assay shows very high sensitivity with IC50 of 0.4 ng/mL and LOD of 0.05 ng/mL when it was run in 0.02 mol/L PBS (pH 7.5). This MAb has shown high specificity to sulfamethazine, with little cross reactivity for sulfamerazine (5.27%) and sulfadimethoxypyrimidine (1.12%) and very low cross reactivity values for the other test compounds (≤0.1%). Sulfamethazine was spiked in milk, honey, and swine urine. After a simple extraction procedure the extracts at appropriate dilution were analyzed by ELISA. Satisfactory results were obtained by this assay, with average recoveries of 95-116% and coefficients of variation (CVs) of 5-9%. These results suggests that the MAb-based ELISA will be a feasible quantitative/screening method for sulfamethazine residue in real samples.

Determination of sulfonamide antibiotics in wastewater: a comparison of solid phase microextraction and solid phase extraction methods.

In recent years, pharmaceutical and personal care products (PPCPs) have been detected in diverse environments (including groundwater, river water, and municipal wastewater). In order to evaluate their environmental impact, PPCPs must first be accurately determined. In this study, we focused on developing methods to accurately determine 10 sulfonamide antibiotics: sulfaguanidine, sulfacetamide, sulfadiazine, sulfathiazine, sulfapyridine, sulfamerazine, sulfamethazine, sulfamethoxazole, sulfadimethoxine, and sulfasalazine. While sulfonamides can easily be determined in pure water, wastewater influent and effluent collected from sewage treatment plants in Burlington and Toronto (Ontario) were found to generate confounding matrix effects. In an effort to overcome these matrix effects, we developed a solid phase microextraction (SPME) method to determine sulfonamides. Of the five different fiber assemblies investigated, the carbowax/divinylbenzene (CW/DVB) fiber produced the optimal response to sulfonamides. The SPME method was further optimized for sorption time (20min), solution salinity (10%, w/v, KCl), pH (4.5), and static desorption time (30min). When compared to solid phase extraction (SPE) using MCX cartridges, we observed that despite having higher MDLs and poorer sensitivity, SPME possessed the advantage of speed and reduced solvent usage. Most importantly, in contrast to SPE, when we applied the SPME method to fortified wastewater samples, we were generally able to accurately determine (i.e., recover) those sulfonamides that were present. Therefore, we conclude that SPME is a viable method for overcoming matrix effects in environmental samples.

Preparation and evaluation of uniform-sized molecularly imprinted polymer beads used for the separation of sulfamethazine.

Uniform-sized molecularly imprinted polymer (MIP) beads were prepared using a one-step swelling and polymerization method. The obtained sulfamethazine (SMZ)-imprinted polymer showed high affinity and selectivity toward SMZ and other structurally related sulfonamides in acetonitrile or water-acetonitrile mobile phases, particularly in high aqueous systems. The column performance of the MIPs for SMZ and its analogues could be improved by elevating the column temperature and optimizing the flow rate. The hydrogen-bonding effect plays a significant role in the recognition process of SMZ-imprinted polymer systems in organic media, while the ion-exchange effect, as well as hydrophobic effect, dominates the retention mechanism in aqueous-rich media, in addition to shape recognition.