The copper complexing of dissolved organic matter released from hydrochar(HDOM)affects the former’s environmental behavior.In this study,how hydrothermal temperatures(180,220 and 260℃)influence the molecular-level c...The copper complexing of dissolved organic matter released from hydrochar(HDOM)affects the former’s environmental behavior.In this study,how hydrothermal temperatures(180,220 and 260℃)influence the molecular-level constitutions and Cu(II)binding features of HDOM were elucidated via fourier transform ion cyclotron resonance mass spectrometry and multi-spectroscopic analysis.The findings demonstrated that the almost HDOM molecules had the traits of lower polarity and higher hydrophobicity.As the hydrothermal temperature increased,the molecules with particularly high relative strength gradually disappeared,average molecular weight,percentages of CHON and aliphatic compounds of HDOM reduced while the percentages of CHO and aromatic compounds increased.In general,the fluorescence quenching of Cu(II)weakened as hydrothermal temperature rose and the Cu(II)binding stability constants of fluorophores in HDOM were 4.50–5.31.In addition,the Cu(II) binding order of fluorophores in HDOM showed temperature heterogeneities, andpolysaccharides or aromatic rings of non-fluorescent substances had the fastest responsesto Cu(II) binding. Generally, fluorescent components tend to bind Cu(II) at relatively traceconcentrations (0–40 μmol/L), whereas non-fluorescent substances tend to the bind Cu(II)at relatively higher concentrations (50–100 μmol/L). This study contributed to the predictionof the potential environmental behaviors and risks of Cu(II) at the molecular level afterhydrochar application.展开更多
The characteristics of effluent organic matter(EfOM) from a wastewater treatment plant(WWTP) during ozonation were investigated using excitation and emission matrix(EEM)spectra, Fourier transform infrared spectroscopy...The characteristics of effluent organic matter(EfOM) from a wastewater treatment plant(WWTP) during ozonation were investigated using excitation and emission matrix(EEM)spectra, Fourier transform infrared spectroscopy(FT-IR) and high-performance size exclusion chromatography(HPSEC) at different ozone dosages. The selectivity of ozonation towards different constituents and functional groups was analysed using two-dimensional correlation spectra(2D-COS) probed by FT-IR, synchronous fluorescence spectra and HPSEC.The results indicated that ozonation can destroy aromatic structures of EfOM and change its molecular weight distribution(MWD). According to 2D-COS analysis, microbial humiclike substances were preferentially removed, and then the protein-like fractions. Terrestrial humic-like components exhibited inactivity towards ozonation compared with the above two fractions. Protein-like substances with small molecular weight were preferentially reacted during ozonation based on 2D-COS probed by HPSEC. In addition, the selectivity of ozone towards different functional groups of EfOM exhibited the following sequence:phenolic and alcoholic C\O groups > aromatic structures containing C_C double bonds >aliphatic C\H. X-ray photoelectron spectroscopy(XPS) further elucidated the preferential reaction of aromatic structures in EfOM during ozonation.展开更多
Metal binding of organic ligands can definitely affect its environmental behavior in waters,while information on the binding heterogeneity with different organic ligands is still lacked till now.In this study,the bind...Metal binding of organic ligands can definitely affect its environmental behavior in waters,while information on the binding heterogeneity with different organic ligands is still lacked till now.In this study,the binding of zinc with organic matters associated with cyanobacterial blooms,including dissolved organic matters（DOM） and attached organic matters（AOM）,were studied by using fluorescence quenching titration combined with two-dimensional correlation spectroscopy（2D-COS）.Metal-induced fluorescent quenching was obviously observed both for DOM and AOM,indicating the formation of metal-ligand complexes.Compared with the one-dimensional spectra,2D-COS revealed the sequences of metal-ligand interaction with the following orders：276 nm 〉 232 ran for DOM and232 nm 〉 276 nm for AOM.Furthermore,the modified Stern-Volmer model showed that the binding constant（logKM） of 276 nm in DOM was higher than that of 232 nm（4.93 vs.4.51）,while AOM was characterized with a high binding affinity for 232 nm（log KM：4.83）.The ranks of log KM values were consistent with the sequential orders derived from 2D-COS results both for the two samples.Fluorescence quenching titration combined with 2D-COS was an effective method to characterize the metal-ligand interaction.展开更多
Liquid state methanol and ethanol under different temperatures have been investigated by FT-NIR(Fourier transform nearinfrared) spectroscopy,generalized two-dimensional(2D) correlation spectroscopy,and PCA(principal c...Liquid state methanol and ethanol under different temperatures have been investigated by FT-NIR(Fourier transform nearinfrared) spectroscopy,generalized two-dimensional(2D) correlation spectroscopy,and PCA(principal component analysis) . First,the FT-NIR spectra were measured over a temperature range of 30-64(or 30-71) °C,and then the 2D correlation spectra were computed.Combining near-infrared spectroscopy,generalized 2D correlation spectroscopy,and references,we analyzed the molecular structures(especially the hydrogen bond) of methanol and ethanol,and performed the NIR band assignments. The PCA method was employed to verify the results of the 2D analysis.This study will be helpful to the understanding of these reagents.展开更多
The generalized two-dimensional correlation analysis based on time-resolved light scattering patterns （2D TRLS） has been employed to study the phase separation process of an epoxy-amine-polyethersulfone blend in whi...The generalized two-dimensional correlation analysis based on time-resolved light scattering patterns （2D TRLS） has been employed to study the phase separation process of an epoxy-amine-polyethersulfone blend in which the secondary phase separation takes place. The results of the 2D TRLS provided more detailed information that was not readily observed in the 1D TRLS patterns. （i） During the first process of phase separation, the sequential order of coarsening in size of the domains among the larger and smaller ones has been reversed between the diffusion regime and the hydrodynamic regime. （ii） The change of the larger domains in size, due to the hydrodynamic flow in the late stage of the first phase separation process, keeps on taking place earlier than that of the new domains appeared in the secondary phase separation process. （iii） During the secondary phase separation process the size growth of the smaller domains takes place earlier than that of the larger ones, probably due to the assumption that the coarsening mode could decrease the interface tension more quickly.展开更多
Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes.However,the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ...Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes.However,the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous.The aim of this study was to use non-destructive measurement methods to investigate the role of MnO_(2) in the evolution of humic substances(HSs)during oxidative polymerization of polyphenol-amino acid.Our results suggested a synergistic effect between MnO_(2) and O_(2) in promoting the polymerization reaction and identified that MnO_(2) alone had a limited ability in accelerating the transformation of fulvic acid(FA)to humic acid(HA),whereas O_(2) was the key factor in the process.Two-dimensional correlation spectroscopy(2D-COS)showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process,indicating the formation of simple organic matter followed by FA and then HA.13C nuclear magnetic resonance(13C NMR)analysis revealed that the products under both air and N2 conditions in the presence of MnO_(2) had greater amounts of aromatic-C than in the absence of MnO_(2),demonstrating that MnO_(2) affected the structure of the humification products.The results of this study provided new insights into the theory of abiotic humification.展开更多
基金supported by the National Natural Science Foundation of China(No.42307090)the Open Subject from State Environmental Protection Key Laboratory of Aquatic Ecosystem Health in theMiddle and Lower Reaches of Yangtze River(No.AEHKF2023008).
文摘The copper complexing of dissolved organic matter released from hydrochar(HDOM)affects the former’s environmental behavior.In this study,how hydrothermal temperatures(180,220 and 260℃)influence the molecular-level constitutions and Cu(II)binding features of HDOM were elucidated via fourier transform ion cyclotron resonance mass spectrometry and multi-spectroscopic analysis.The findings demonstrated that the almost HDOM molecules had the traits of lower polarity and higher hydrophobicity.As the hydrothermal temperature increased,the molecules with particularly high relative strength gradually disappeared,average molecular weight,percentages of CHON and aliphatic compounds of HDOM reduced while the percentages of CHO and aromatic compounds increased.In general,the fluorescence quenching of Cu(II)weakened as hydrothermal temperature rose and the Cu(II)binding stability constants of fluorophores in HDOM were 4.50–5.31.In addition,the Cu(II) binding order of fluorophores in HDOM showed temperature heterogeneities, andpolysaccharides or aromatic rings of non-fluorescent substances had the fastest responsesto Cu(II) binding. Generally, fluorescent components tend to bind Cu(II) at relatively traceconcentrations (0–40 μmol/L), whereas non-fluorescent substances tend to the bind Cu(II)at relatively higher concentrations (50–100 μmol/L). This study contributed to the predictionof the potential environmental behaviors and risks of Cu(II) at the molecular level afterhydrochar application.
基金supported by the National Key Technology Support Program (No.2014BAC13B06)the National Natural Science Foundation of China (Nos.51708443,51378414)+2 种基金the National Key Research and Development Program of China (No.2016YFC0400701)the China Postdoctoral Science Foundation (No.2017M623326XB)the Program for Innovative Research Teams in Shaanxi (No.2013KCT-13)
文摘The characteristics of effluent organic matter(EfOM) from a wastewater treatment plant(WWTP) during ozonation were investigated using excitation and emission matrix(EEM)spectra, Fourier transform infrared spectroscopy(FT-IR) and high-performance size exclusion chromatography(HPSEC) at different ozone dosages. The selectivity of ozonation towards different constituents and functional groups was analysed using two-dimensional correlation spectra(2D-COS) probed by FT-IR, synchronous fluorescence spectra and HPSEC.The results indicated that ozonation can destroy aromatic structures of EfOM and change its molecular weight distribution(MWD). According to 2D-COS analysis, microbial humiclike substances were preferentially removed, and then the protein-like fractions. Terrestrial humic-like components exhibited inactivity towards ozonation compared with the above two fractions. Protein-like substances with small molecular weight were preferentially reacted during ozonation based on 2D-COS probed by HPSEC. In addition, the selectivity of ozone towards different functional groups of EfOM exhibited the following sequence:phenolic and alcoholic C\O groups > aromatic structures containing C_C double bonds >aliphatic C\H. X-ray photoelectron spectroscopy(XPS) further elucidated the preferential reaction of aromatic structures in EfOM during ozonation.
基金funded by the National Natural Science Foundation of China(Nos.51479187,51209192)the China Postdoctoral Science Foundation(Nos.2014T70505+1 种基金2013M 540438)the PAPD,and the State Key Laboratory of Pollution Control and Resource Reuse Foundation(No.PCRRF13011)
文摘Metal binding of organic ligands can definitely affect its environmental behavior in waters,while information on the binding heterogeneity with different organic ligands is still lacked till now.In this study,the binding of zinc with organic matters associated with cyanobacterial blooms,including dissolved organic matters（DOM） and attached organic matters（AOM）,were studied by using fluorescence quenching titration combined with two-dimensional correlation spectroscopy（2D-COS）.Metal-induced fluorescent quenching was obviously observed both for DOM and AOM,indicating the formation of metal-ligand complexes.Compared with the one-dimensional spectra,2D-COS revealed the sequences of metal-ligand interaction with the following orders：276 nm 〉 232 ran for DOM and232 nm 〉 276 nm for AOM.Furthermore,the modified Stern-Volmer model showed that the binding constant（logKM） of 276 nm in DOM was higher than that of 232 nm（4.93 vs.4.51）,while AOM was characterized with a high binding affinity for 232 nm（log KM：4.83）.The ranks of log KM values were consistent with the sequential orders derived from 2D-COS results both for the two samples.Fluorescence quenching titration combined with 2D-COS was an effective method to characterize the metal-ligand interaction.
基金supported by the Medical Scientific Research Foundation of Guangdong Province,China(B2009043)
文摘Liquid state methanol and ethanol under different temperatures have been investigated by FT-NIR(Fourier transform nearinfrared) spectroscopy,generalized two-dimensional(2D) correlation spectroscopy,and PCA(principal component analysis) . First,the FT-NIR spectra were measured over a temperature range of 30-64(or 30-71) °C,and then the 2D correlation spectra were computed.Combining near-infrared spectroscopy,generalized 2D correlation spectroscopy,and references,we analyzed the molecular structures(especially the hydrogen bond) of methanol and ethanol,and performed the NIR band assignments. The PCA method was employed to verify the results of the 2D analysis.This study will be helpful to the understanding of these reagents.
基金supported by the National Natural Science of Foundation of China(NSFC)(Nos.20674014, 20425415,20274010,50103003,20221402)
文摘The generalized two-dimensional correlation analysis based on time-resolved light scattering patterns （2D TRLS） has been employed to study the phase separation process of an epoxy-amine-polyethersulfone blend in which the secondary phase separation takes place. The results of the 2D TRLS provided more detailed information that was not readily observed in the 1D TRLS patterns. （i） During the first process of phase separation, the sequential order of coarsening in size of the domains among the larger and smaller ones has been reversed between the diffusion regime and the hydrodynamic regime. （ii） The change of the larger domains in size, due to the hydrodynamic flow in the late stage of the first phase separation process, keeps on taking place earlier than that of the new domains appeared in the secondary phase separation process. （iii） During the secondary phase separation process the size growth of the smaller domains takes place earlier than that of the larger ones, probably due to the assumption that the coarsening mode could decrease the interface tension more quickly.
基金This manuscript is based on work supported by the National Key R&D Program of China(No.2018YFC1901405)。
文摘Abiotic humification is important in the formation and evolution of organic matter in soil and compost maturing processes.However,the roles of metal oxides in abiotic humification reactions under micro-aerobic remain ambiguous.The aim of this study was to use non-destructive measurement methods to investigate the role of MnO_(2) in the evolution of humic substances(HSs)during oxidative polymerization of polyphenol-amino acid.Our results suggested a synergistic effect between MnO_(2) and O_(2) in promoting the polymerization reaction and identified that MnO_(2) alone had a limited ability in accelerating the transformation of fulvic acid(FA)to humic acid(HA),whereas O_(2) was the key factor in the process.Two-dimensional correlation spectroscopy(2D-COS)showed that the evolution in the UV-vis spectra followed the order of 475–525 nm>300–400 nm>240–280 nm in the humification process,indicating the formation of simple organic matter followed by FA and then HA.13C nuclear magnetic resonance(13C NMR)analysis revealed that the products under both air and N2 conditions in the presence of MnO_(2) had greater amounts of aromatic-C than in the absence of MnO_(2),demonstrating that MnO_(2) affected the structure of the humification products.The results of this study provided new insights into the theory of abiotic humification.
