Defluoridation of coal mining water is of great significance for sustainable development of coal industry in western China.A novel one-step mechanochemical method was developed to prepare polymeric aluminum modified p...Defluoridation of coal mining water is of great significance for sustainable development of coal industry in western China.A novel one-step mechanochemical method was developed to prepare polymeric aluminum modified powder activated carbon(PAC)for effective fluoride removal from coal mining water.Aluminum was stably loaded on the PAC through facile solid-phase reaction between polymeric aluminum(polyaluminum chloride(PACl)or polyaluminum ferric chloride(PAFC))and PAC(1:15 W/W).Fluoride adsorption on PACl and PAFC modified PAC(C-PACl and C-PAFC)all reached equilibrium within 5 min,at rate of 2.56 g mg^(-1)sec^(-1)and 1.31 g mg^(-1)sec^(-1)respectively.Larger increase of binding energy of Al on C-PACl(Al–F bond:76.64 eV and Al–FOH bond:77.70 eV)relative to that of Al on C-PAFC(Al–F bond:76.52 eV)explained higher fluoride uptake capacity of C-PACl.Less chloride was released from C-PACl than that from C-PAFC due to its higher proportion of covalent chlorine and lower proportion of ionic chlorine.The elements mapping and atomic composition proved the stability of Al loaded on the PAC as well as the enrichment of fluoride on both CPACl and C-PAFC.The Bader charge,formation energy and bond length obtained from DFT computational results explained the fluoride adsorption mechanism further.The carbon emission was 7.73 kg CO_(2)-eq/kg adsorbent prepared through mechanochemical process,which was as low as 1:82.3 to 1:8.07×10^(4)compared with the ones prepared by conventional hydrothermal methods.展开更多
Organofluorinated surfactants are widely employed in textile finishing agents (TFAs) to achieve oil, water, and stain repellency. This has been regarded as an important emission source of per-and polyfluoroalkyl subst...Organofluorinated surfactants are widely employed in textile finishing agents (TFAs) to achieve oil, water, and stain repellency. This has been regarded as an important emission source of per-and polyfluoroalkyl substances (PFASs) to the environment. China is the biggest manufacturer of clothes, and thus TFA production is also a relevant industrial activity. Nevertheless, to date, no survey has been conducted on PFAS contents in commercially available TFAs. In the present study, TFA products were investigated by the Kendrick mass defect method. The quantification results demonstrated a significant presence of perfluorooctane sulfonate (0.37 mg/L) in TFAs manufactured by electrochemical fluorination technology. The products obtained by short-chain PFAS-based telomerization were dominated by perfluorooctanoic acid (mean concentration: 0.29 mg/L), whose values exceeded the limits stated in the European Chemical Agency guidelines (0.025 mg/L). Moreover, the total oxidizable precursor assay indicated high levels of indirectly quantified precursors with long alkyl chains (C7–C9). Together, these results suggest that there is currently a certain of environmental and health risks in China that originates from the utilization of TFAs, and a better manufacturing processes are required to reduce such risks.展开更多
Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonl...Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU^-, 5-FU^2-, CAP, and CAP^- were determined to be 7.07(±0.11)×10^4 M^-1·s^-1,1.36(±0.06)×10^6 M^-1·s^-1,2.62(±0.17)×10^7M^-1·s^-1,9.69(±0.08)×10^3M^-1·s^-1,and 4.28(±0.07)×10^5M^-1·s^-1, respectively;furthermore, the second-order rate constants for *OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10^9 M^-1·s^-1 and 9.95(±0.26)×10^9M^-1·s^-1, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation;however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibriofischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.展开更多
基金supported by the National Natural Science Foundation of China(No.52100070)the Science and Technology Innovation Project of China Energy Investment Corporation(No.SZY93002219N).
文摘Defluoridation of coal mining water is of great significance for sustainable development of coal industry in western China.A novel one-step mechanochemical method was developed to prepare polymeric aluminum modified powder activated carbon(PAC)for effective fluoride removal from coal mining water.Aluminum was stably loaded on the PAC through facile solid-phase reaction between polymeric aluminum(polyaluminum chloride(PACl)or polyaluminum ferric chloride(PAFC))and PAC(1:15 W/W).Fluoride adsorption on PACl and PAFC modified PAC(C-PACl and C-PAFC)all reached equilibrium within 5 min,at rate of 2.56 g mg^(-1)sec^(-1)and 1.31 g mg^(-1)sec^(-1)respectively.Larger increase of binding energy of Al on C-PACl(Al–F bond:76.64 eV and Al–FOH bond:77.70 eV)relative to that of Al on C-PAFC(Al–F bond:76.52 eV)explained higher fluoride uptake capacity of C-PACl.Less chloride was released from C-PACl than that from C-PAFC due to its higher proportion of covalent chlorine and lower proportion of ionic chlorine.The elements mapping and atomic composition proved the stability of Al loaded on the PAC as well as the enrichment of fluoride on both CPACl and C-PAFC.The Bader charge,formation energy and bond length obtained from DFT computational results explained the fluoride adsorption mechanism further.The carbon emission was 7.73 kg CO_(2)-eq/kg adsorbent prepared through mechanochemical process,which was as low as 1:82.3 to 1:8.07×10^(4)compared with the ones prepared by conventional hydrothermal methods.
文摘Organofluorinated surfactants are widely employed in textile finishing agents (TFAs) to achieve oil, water, and stain repellency. This has been regarded as an important emission source of per-and polyfluoroalkyl substances (PFASs) to the environment. China is the biggest manufacturer of clothes, and thus TFA production is also a relevant industrial activity. Nevertheless, to date, no survey has been conducted on PFAS contents in commercially available TFAs. In the present study, TFA products were investigated by the Kendrick mass defect method. The quantification results demonstrated a significant presence of perfluorooctane sulfonate (0.37 mg/L) in TFAs manufactured by electrochemical fluorination technology. The products obtained by short-chain PFAS-based telomerization were dominated by perfluorooctanoic acid (mean concentration: 0.29 mg/L), whose values exceeded the limits stated in the European Chemical Agency guidelines (0.025 mg/L). Moreover, the total oxidizable precursor assay indicated high levels of indirectly quantified precursors with long alkyl chains (C7–C9). Together, these results suggest that there is currently a certain of environmental and health risks in China that originates from the utilization of TFAs, and a better manufacturing processes are required to reduce such risks.
文摘Anticancer drugs (ADs) have been detected in the environment and represent a risk to aquatic organisms, necessitating AD removal in drinking water and wastewater treatment. In this study, ozonation of the most commonly used antimetabolite ADs, namely 5-fluorouracil (5-FU) and its prodrug capecitabine (CAP), was investigated to determine reaction kinetics, oxidation mechanisms, and residual toxicity. The specific second-order rate constants between aqueous ozone and 5-FU, 5-FU^-, 5-FU^2-, CAP, and CAP^- were determined to be 7.07(±0.11)×10^4 M^-1·s^-1,1.36(±0.06)×10^6 M^-1·s^-1,2.62(±0.17)×10^7M^-1·s^-1,9.69(±0.08)×10^3M^-1·s^-1,and 4.28(±0.07)×10^5M^-1·s^-1, respectively;furthermore, the second-order rate constants for *OH reaction with 5-FU and CAP at pH 7 were determined to be 1.85(±0.20)×10^9 M^-1·s^-1 and 9.95(±0.26)×10^9M^-1·s^-1, respectively. Density functional theory was used to predict the main ozone reaction sites of 5-FU (olefin) and CAP (olefin and deprotonated secondary amine), and these mechanisms were supported by the identified transformation products. Carboxylic acids constituted a majority of the residual organic matter for 5-FU ozonation;however, carboxylic acids and aldehydes were important components of the residual organic matter generated by CAP. Ozone removed the toxicity of 5-FU to Vibriofischeri, but the residual toxicity of ozonated CAP solutions exhibited an initial increase before subsequent removal. Ultimately, these results suggest that ozone is a suitable technology for treatment of 5-FU and CAP, although the residual toxicity of transformation products must be carefully considered.