Phosphorus and nitrogen transformation in antibiotic mycelial residue derived hydrochar and activated pyrolyzed samples: Effect on Pb (II) immobilization.

In this study, lincomycin residue (LR, a type of antibiotic mycelial residue) derived hydrochar samples (LR-HCs) were obtained from hydrothermal carbonization (HTC), and pyrolysis applied to these LR-HCs to produce activated pyrolyzed samples (LR-APs). Transformation of phosphorus (P) and nitrogen (N) species during HTC and pyrolysis was of primary interest and characterized by several techniques. Nitrogen content of dry LR was calculated by elemental analysis, being 7.91 wt. %, decreasing to 2.51 after HTC and 1.12 wt. % after concesutive HTC and pyrolysis. FT-IR analysis provided evidence for amine groups in LR samples. XPS analysis described N species (Pyridinic-N, Amine-N, Protein-N, Pyrrolic-N, and Quaternary-N) and P species (ortho-P/pyro-P and Ar-P) in LR samples, effectively. Sequential extraction showed that the HTC and pyrolysis changed the proportion of the P species from labile (P-NaHCO3 and P-NaOH) to stable ones (P-residue). Utilization and suitability of as-prepared LR-HCs and LR-APs for heavy metal Pb (II) immobilization show promising results. To help understand immobilization process, kinetic (pseudo-1st-order and pseudo-2nd-order) and isotherm (Freundlich) models were tested and verified. Results confirmed that P and N species were transformed during HTC and pyrolysis and that these processes lead to an advantageous effect on Pb (II) removal from solution.

Conversion of phosphorus and nitrogen in lincomycin residue during microwave-assisted hydrothermal liquefaction and its application for Pb2+ removal.

Treatment of antibiotic fermentative residue (AFR) produced from pharmaceutical industries and their application in the environment has been gaining researchers' interest. In this study, lincomycin residue (LMR, the type of AFR) was treated with microwave-assisted hydrothermal liquefaction (MW-HTL) in a temperature range 120-210 °C, transforming effect of phosphorus (P) and nitrogen (N) functional groups in LMR samples was characterized with elemental analysis, XRD, XPS, FT-IR, and P-extraction, and utilized LMR samples for Pb2+ removal from aqueous solutions. The temperature had a significant impact on P and N functional groups conversion justified by characterization techniques and also responsible for Pb2+ adsorption. LMR hydrochar produced at 210 °C was accounted highest Pb2+ adsorption capacity (57.4 mg g-1), higher four folds than raw LMR (13.8 mg g-1). To understand the mechanism and rate defining phase of adsorption equilibrium isotherm and kinetic models were applied systematically. Adsorption results of LMR and its derived hydrochar samples found connectivity with Langmuir and pseudo-first-order isotherm models. Adsorption mainly occurred as ion-exchange dependent on the substitution of metal ions (Pb2+) to Ca2+ ions present in P-materials, and surface adsorption dependent on surface functional groups of LMR samples. Better operation feasibility of MW-HTL treated LMR, elaboration of P and N conversion behavior and high sorption of Pb2+ ions could make LMR a frontrunner for heavy metals immobilization.

Oxidation of antibiotics during water treatment with potassium permanganate: reaction pathways and deactivation.

Recent work demonstrates that three widely administered antibiotics (ciprofloxacin, lincomycin, and trimethoprim) are oxidized by potassium permanganate [KMnO(4), Mn(VII)] under conditions relevant to water treatment operations. However, tests show that little to no mineralization occurs during reactions with Mn(VII), so studies were undertaken to characterize the reaction products and pathways and to assess the effects of Mn(VII)-mediated transformations on the antibacterial activity of solutions. Several oxidation products were identified for each antibiotic by liquid chromatography-tandem mass spectrometry (LC-MS/MS). For ciprofloxacin, 12 products were identified, consistent with oxidation of the tertiary aromatic and secondary aliphatic amine groups on the piperazine ring and the cyclopropyl group. For lincomycin, seven products were identified that indicate structural changes to the pyrrolidine ring and thioether group. For trimethoprim, seven products were identified, consistent with Mn(VII) reaction at C═C double bonds on the pyrimidine ring and the bridging methylene group. Oxidation pathways are proposed based on the identified products. Bacterial growth inhibition bioassays (E. coli DH5α) show that the mixture of products resulting from Mn(VII) reactions with the antibiotics collectively retain negligible antibacterial potency in comparison to the parent antibiotics. These results suggest that permanganate can be an effective reagent for eliminating the pharmaceutical activity of selected micropollutants during drinking water treatment.

Oxidation kinetics of antibiotics during water treatment with potassium permanganate.

The ubiquitous occurrence of antibiotics in aquatic environments raises concerns about potential adverse effects on aquatic ecology and human health, including the promotion of increased antibiotic resistance. This study examined the oxidation of three widely detected antibiotics (ciprofloxacin, lincomycin, and trimethoprim) by potassium permanganate [KMnO(4); Mn(VII)]. Reaction kinetics were described by second-order rate laws, with apparent second-order rate constants (k(2)) at pH 7 and 25 degrees C in the order of 0.61 +/- 0.02 M(-1) s(-1) (ciprofloxacin) < 1.6 +/- 0.1 M(-1) s(-1) (trimethoprim) < 3.6 +/- 0.1 M(-1) s(-1) (lincomycin). Arrhenius temperature dependence was observed with apparent activation energies (E(a)) ranging from 49 kJ mol(-1) (trimethoprim) to 68 kJ mol(-1) (lincomycin). Rates of lincomycin and trimethoprim oxidation exhibited marked pH dependences, whereas pH had only a small effect on rates of ciprofloxacin oxidation. The effects of pH were quantitatively described by considering parallel reactions between KMnO(4) and individual acid-base species of the target antibiotics. Predictions from a kinetic model that included temperature, KMnO(4) dosage, pH, and source water oxidant demand as input parameters agreed reasonably well with measurements of trimethoprim and lincomycin oxidation in six drinking water utility sources. Although Mn(VII) reactivity with the antibiotics was lower than that reported for ozone and free chlorine, its high selectivity and stability suggests a promising oxidant for treating sensitive micropollutants in organic-rich matrices (e.g., wastewater).

Quantitative analysis of lincomycin in animal tissues and bovine milk by liquid chromatography electrospray ionization tandem mass spectrometry.

A sensitive method for determining lincomycin in bovine milk, animal muscles and organs using liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI/MS/MS) is presented. Milk and homogenized animal tissues were extracted with acetonitrile twice after addition of an appropriate amount of clindamycin, a lincosamide analogue as the internal standard. The combined extracts were finally made up to 10 ml with distilled water and partitioned with hexane to remove the animal fats prior to analysis. Analytes in the extracts were separated on a reversed phase C18 column (250 mm x 2.1 mm, 5 microm) using a mobile phase of a 3:7 (v/v) mixture of 0.1% formic acid in acetonitrile and an ammonium formate buffer (ammonium formate:formic acid:acetonitrile:water, 1:5:50:950, v/v/v/v) running at a flow rate of 0.2 ml min(-1). Presence of lincomycin was confirmed by the presence of two characteristic product ions at m/z 126.1 and 359.2 within a defined retention time window from the precursor ion at m/z 407.2, whilst quantification was based on the relative ratio of the sum of the peak areas at m/z 126.1 and 359.2 for lincomycin to that of the internal standard (peaks at m/z 126.1 and 377.2) with reference to the respective ratios of the calibration standards. The validated method that was found to have linear responses in the calibration range from 25 to 3000 microg kg(-1) and satisfactory intra-day and inter-day accuracy (94.4-107.8%) and precision (1.3-7.8%) at concentrations ranging from 100 to 1500 microg kg(-1) has been applied to real samples and matrix spiked samples. It is considered robust and suitable for analysis of lincomycin in milk and animal tissues.