Metal oxides with oxygen vacancies have a significant impact on catalytic activity for the transformation of organic pollutants in waste-to-energy(WtE)incineration processes.This study aims to investigate the influenc...Metal oxides with oxygen vacancies have a significant impact on catalytic activity for the transformation of organic pollutants in waste-to-energy(WtE)incineration processes.This study aims to investigate the influence of hematite surface oxygen point defects on the formation of environmentally persistent free radicals(EPFRs)from phenolic compounds based on the first-principles calculations.Two oxygen-deficient conditions were considered:oxygen vacancies at the top surface and on the subsurface.Our simulations indicate that the adsorption strength of phenol on theα-Fe_(2)O_(3)(0001)surface is enhanced by the presence of oxygen vacancies.However,the presence of oxygen vacancies has a negative impact on the dissociation of the phenol molecule,particularly for the surface with a defective point at the top layer.Thermo-kinetic parameters were established over a temperature range of300-1000 K,and lower reaction rate constants were observed for the scission of phenolic O-H bonds over the oxygen-deficient surfaces compared to the pristine surface.The negative effects caused by the oxygen-deficient conditions could be attributed to the local reduction of FeⅢto FeⅡ,which lower the oxidizing ability of surface reaction sites.The findings of this study provide us a promising approach to regulate the formation of EPFRs.展开更多
The outbreak of COVID-19 has caused concerns globally.To reduce the rapid transmission of the virus,strict city lockdown measures were conducted in different regions.China is the country that takes the earliest home-b...The outbreak of COVID-19 has caused concerns globally.To reduce the rapid transmission of the virus,strict city lockdown measures were conducted in different regions.China is the country that takes the earliest home-based quarantine for people.Although normal industrial and social activities were suspended,the spread of virus was efficiently controlled.Simultaneously,another merit of the city lockdown measure was noticed,which is the improvement of the air quality.Contamination levels of multiple atmospheric pollutants were decreased.However,in this work,24 and 14 air fine particulate matter(PM_(2.5))samples were continuously collected before and during COVID-19 city lockdown in Linfen(a typical heavy industrial city in China),and intriguingly,the unreduced concentration was found for environmentally persistent free radicals(EPFRs)in PM_(2.5)after normal life suspension.The primary non-stopped coal combustion source and secondary Cu-related atmospheric reaction may have impacts on this phenomenon.The cigarette-based assessment model also indicated possible exposure risks of PM_(2.5)-bound EPFRs during lockdown of Linfen.This study revealed not all the contaminants in the atmosphere had an apparent concentration decrease during city lockdown,suggesting the pollutants with complicated sources and formation mechanisms,like EPFRs in PM_(2.5),still should not be ignored.展开更多
Background,aim,and scope Environmentally persistent free radicals(EPFRs)have received significant attention due to their longer lifetime and stable existence in various environments.The strong environmental migration ...Background,aim,and scope Environmentally persistent free radicals(EPFRs)have received significant attention due to their longer lifetime and stable existence in various environments.The strong environmental migration ability of particulate matter allows EPFRs to migrate over long-distance transport,thereby impacting the quality of the local atmospheric environment.Additionally,EPFRs can also adhere to atmospheric particles and interact with typical gaseous pollutants to affect atmospheric chemical reactions.EPFRs can produce some reactive organic species,promoting oxidative stress in the human body,damaging biological macromolecules and ultimately affecting the organism health.EPFRs are considered as a novel type of pollutant that affects human health.Despite their significance,there are few literatures available on the characteristics and fate behaviors of EPFRs up to date.Therefore,supplemental reviews are crucial for providing comprehensive understanding of EPFRs.Materials and methods This review summarizes the characteristics of EPFRs in particulate matter,outlines the generation mechanism and influencing factors of EPFRs,and the impacts of EPFRs on environmental quality and organism health.Results The content of EPFRs in particulate matter ranges from 1017 to 1020 spins∙g−1.Due to the strong mobility of atmospheric particulate matter,the long-term exposure to high levels of EPFRs may aggravate the impact of particulate matter on human health.The interaction between EPFRs and typical gaseous pollutants can alter their fate and influence atmospheric chemical reactions.EPFRs are mainly produced by transition metal elements and substituted aromatic hydrocarbons through electron transfer.Additionally,the chemical bond rupture of organic substances through heat treatment or ultraviolet radiation can also produce EPFRs,and heterogeneous reactions are capable producing them as well.The production of EPFRs is not only influenced by transition metal elements and precursors,but also by various environmental factors such as oxygen,temperature,light radiation,and relative humidity.Discussion EPFRs in atmospheric particulates matters are usually rich in fine particulates with obvious seasonal and regional variations.They can easily enter the human respiratory tract and lungs with inhalable particulates,thereby increasing the risk of exposure.Additionally,EPFRs in atmospheric particulates can interact with some typical gaseous pollutants,impacting the life and fate of EPFRs in the atmosphere,and alter atmospheric chemical reactions.Traditionally,EPFRs are generated by transition metal elements and substituted aromatic hydrocarbons undergoing electron transfer in the post-flame and cool-zone regions of combustion systems and other thermal processes to remove HCl,H_(2)O or CO groups,ultimately produce semiquinones,phenoxyls,and cyclopentadienyls.Recent studies have indicated that EPFRs can also be generated under the conditions of without transition metal elemental.Organics can also produce EPFRs through chemical bond rupture during heat treatment or light radiation conditions,as well as through some heterogeneous reactions and photochemical secondary generation of EPFRs.The presence or absence of oxygen has different effects on the type and yield of EPFRs.The concentration,type,and crystal type of transition metal elements will affect the type,content,and atmospheric lifetime of EPFRs.It is generally believed that the impact of transition metal element types on EPFRs is related to the oxidation-reduction potential.The combustion temperature or heat treatment process significantly affects the type and amount of EPFRs.Factors such as precursor loading content,pH conditions,light radiation and relative humidity also influence the generation of EPFRs.EPFRs can interact with pollutants in the environment during their migration and transformation process in environmental medium.This process accelerates the degradation of pollutants and plays a crucial role in the migration and transformation of organic pollutants in environmental media.The reaction process of EPFRs may lead to the production of reactive oxygen species(ROS)such as∙OH,which can induce oxidative stress,inflammation and immune response to biological lung cells and tissues,leading to chronic respiratory and cardiopulmonary dysfunction,cardiovascular damage and neurotoxic effects,ultimately impacting the health of organisms.Conclusions The interaction mechanism between EPFRs in particulate matter and gaseous pollutants remains unclear.Furthermore,research on the generation mechanism of EPFRs without the participation of transition metals is not comprehensive,and the detection of EPFRs is limited to simple qualitative categories and lack accurate qualitative analysis.Recommendations and perspectives Further research should be conducted on the generation mechanism,measurement techniques,migration pathways,and transformation process of EPFRs.It is also important to explore the interaction between EPFRs in atmospheric particulate matter and typical gaseous pollutants.展开更多
To reveal the influence of the diversity of precursors on the formation of environmental persistent free radicals(EPFRs),pomelo peel(PP)and its physically divided portion,pomelo cuticle(PC),and white fiber(WF)were use...To reveal the influence of the diversity of precursors on the formation of environmental persistent free radicals(EPFRs),pomelo peel(PP)and its physically divided portion,pomelo cuticle(PC),and white fiber(WF)were used as precursors to prepare six hydrochars:PPH-Fe,PCH-Fe,WFH-Fe,PPH,PCH,and WFH with and without Fe(III)addition during hydrothermal carbonization(HTC).PPH-Fe and WFH-Fe had higher EPFRs content(9.11×10^(18)and 8.25×10^(18)spins·g^(−1))compared to PPH and WFH(3.33×10^(18)and 2.96×10^(18)spins·g^(−1)),indicating that iron-doping favored EPFRs formation.However,PCH-Fe had lower EPFRs content(2.78×10^(18)spins·g^(−1))than PCH(7.95×10^(18)spins·g^(−1)),possibly due to excessive iron leading to the consumption of the generated EPFRs.For another reason,the required Fe(III)amount for EPFRs formation might vary among different precursors.PC has a lower concentration of phenolic compounds but 68-97%fatty acids,while WF and PP are rich in cellulose and lignin.In the Fenton-like reaction,oxygen-centered radicals of hydrochar played a significant role in activating H_(2)O_(2)and efficiently degrading bisphenol A(BPA).Mechanisms of reactive oxygen species(ROS)generation in hydrochar/H_(2)O_(2)system were proposed.EPFRs on hydrochar activate H_(2)O_(2)via electron transfer,creating·OH and 1O2,leading to BPA degradation.More importantly,the embedded EPFRs on the hydrochar’s inner surface contributed to the prolonged Fenton-like reactivity of PPH-Fe stored for 45 days.This study demonstrates that by optimizing precursor selection and iron doping,hydrochars can be engineered to maximize their EPFRs content and reactivity,providing a cost-effective solution for the degradation of hazardous pollutants.展开更多
基金supported by the National Natural Science Foundation of China(Nos.21976206,22136001,22276197,92143201)the National Key Research and Development Program of China(No.2020YFA0907500)the Beijing Natural Science Foundation(No.JQ22027)。
文摘Metal oxides with oxygen vacancies have a significant impact on catalytic activity for the transformation of organic pollutants in waste-to-energy(WtE)incineration processes.This study aims to investigate the influence of hematite surface oxygen point defects on the formation of environmentally persistent free radicals(EPFRs)from phenolic compounds based on the first-principles calculations.Two oxygen-deficient conditions were considered:oxygen vacancies at the top surface and on the subsurface.Our simulations indicate that the adsorption strength of phenol on theα-Fe_(2)O_(3)(0001)surface is enhanced by the presence of oxygen vacancies.However,the presence of oxygen vacancies has a negative impact on the dissociation of the phenol molecule,particularly for the surface with a defective point at the top layer.Thermo-kinetic parameters were established over a temperature range of300-1000 K,and lower reaction rate constants were observed for the scission of phenolic O-H bonds over the oxygen-deficient surfaces compared to the pristine surface.The negative effects caused by the oxygen-deficient conditions could be attributed to the local reduction of FeⅢto FeⅡ,which lower the oxidizing ability of surface reaction sites.The findings of this study provide us a promising approach to regulate the formation of EPFRs.
基金supported by the National Natural Science Foundation of China (Nos.22106129,22076174 and 91843301)。
文摘The outbreak of COVID-19 has caused concerns globally.To reduce the rapid transmission of the virus,strict city lockdown measures were conducted in different regions.China is the country that takes the earliest home-based quarantine for people.Although normal industrial and social activities were suspended,the spread of virus was efficiently controlled.Simultaneously,another merit of the city lockdown measure was noticed,which is the improvement of the air quality.Contamination levels of multiple atmospheric pollutants were decreased.However,in this work,24 and 14 air fine particulate matter(PM_(2.5))samples were continuously collected before and during COVID-19 city lockdown in Linfen(a typical heavy industrial city in China),and intriguingly,the unreduced concentration was found for environmentally persistent free radicals(EPFRs)in PM_(2.5)after normal life suspension.The primary non-stopped coal combustion source and secondary Cu-related atmospheric reaction may have impacts on this phenomenon.The cigarette-based assessment model also indicated possible exposure risks of PM_(2.5)-bound EPFRs during lockdown of Linfen.This study revealed not all the contaminants in the atmosphere had an apparent concentration decrease during city lockdown,suggesting the pollutants with complicated sources and formation mechanisms,like EPFRs in PM_(2.5),still should not be ignored.
文摘Background,aim,and scope Environmentally persistent free radicals(EPFRs)have received significant attention due to their longer lifetime and stable existence in various environments.The strong environmental migration ability of particulate matter allows EPFRs to migrate over long-distance transport,thereby impacting the quality of the local atmospheric environment.Additionally,EPFRs can also adhere to atmospheric particles and interact with typical gaseous pollutants to affect atmospheric chemical reactions.EPFRs can produce some reactive organic species,promoting oxidative stress in the human body,damaging biological macromolecules and ultimately affecting the organism health.EPFRs are considered as a novel type of pollutant that affects human health.Despite their significance,there are few literatures available on the characteristics and fate behaviors of EPFRs up to date.Therefore,supplemental reviews are crucial for providing comprehensive understanding of EPFRs.Materials and methods This review summarizes the characteristics of EPFRs in particulate matter,outlines the generation mechanism and influencing factors of EPFRs,and the impacts of EPFRs on environmental quality and organism health.Results The content of EPFRs in particulate matter ranges from 1017 to 1020 spins∙g−1.Due to the strong mobility of atmospheric particulate matter,the long-term exposure to high levels of EPFRs may aggravate the impact of particulate matter on human health.The interaction between EPFRs and typical gaseous pollutants can alter their fate and influence atmospheric chemical reactions.EPFRs are mainly produced by transition metal elements and substituted aromatic hydrocarbons through electron transfer.Additionally,the chemical bond rupture of organic substances through heat treatment or ultraviolet radiation can also produce EPFRs,and heterogeneous reactions are capable producing them as well.The production of EPFRs is not only influenced by transition metal elements and precursors,but also by various environmental factors such as oxygen,temperature,light radiation,and relative humidity.Discussion EPFRs in atmospheric particulates matters are usually rich in fine particulates with obvious seasonal and regional variations.They can easily enter the human respiratory tract and lungs with inhalable particulates,thereby increasing the risk of exposure.Additionally,EPFRs in atmospheric particulates can interact with some typical gaseous pollutants,impacting the life and fate of EPFRs in the atmosphere,and alter atmospheric chemical reactions.Traditionally,EPFRs are generated by transition metal elements and substituted aromatic hydrocarbons undergoing electron transfer in the post-flame and cool-zone regions of combustion systems and other thermal processes to remove HCl,H_(2)O or CO groups,ultimately produce semiquinones,phenoxyls,and cyclopentadienyls.Recent studies have indicated that EPFRs can also be generated under the conditions of without transition metal elemental.Organics can also produce EPFRs through chemical bond rupture during heat treatment or light radiation conditions,as well as through some heterogeneous reactions and photochemical secondary generation of EPFRs.The presence or absence of oxygen has different effects on the type and yield of EPFRs.The concentration,type,and crystal type of transition metal elements will affect the type,content,and atmospheric lifetime of EPFRs.It is generally believed that the impact of transition metal element types on EPFRs is related to the oxidation-reduction potential.The combustion temperature or heat treatment process significantly affects the type and amount of EPFRs.Factors such as precursor loading content,pH conditions,light radiation and relative humidity also influence the generation of EPFRs.EPFRs can interact with pollutants in the environment during their migration and transformation process in environmental medium.This process accelerates the degradation of pollutants and plays a crucial role in the migration and transformation of organic pollutants in environmental media.The reaction process of EPFRs may lead to the production of reactive oxygen species(ROS)such as∙OH,which can induce oxidative stress,inflammation and immune response to biological lung cells and tissues,leading to chronic respiratory and cardiopulmonary dysfunction,cardiovascular damage and neurotoxic effects,ultimately impacting the health of organisms.Conclusions The interaction mechanism between EPFRs in particulate matter and gaseous pollutants remains unclear.Furthermore,research on the generation mechanism of EPFRs without the participation of transition metals is not comprehensive,and the detection of EPFRs is limited to simple qualitative categories and lack accurate qualitative analysis.Recommendations and perspectives Further research should be conducted on the generation mechanism,measurement techniques,migration pathways,and transformation process of EPFRs.It is also important to explore the interaction between EPFRs in atmospheric particulate matter and typical gaseous pollutants.
基金supported by the National Key Research and Development Program of China(No.2020YFC1808103)Science&Technology Commission of Shanghai Municipality(No.22002400500)+1 种基金National Natural Science Foundation of China(20907029 and 21577085)Natural Science Fund Projects of Shanghai Municipal Science and Technology Commission(No.14ZR1415600).
文摘To reveal the influence of the diversity of precursors on the formation of environmental persistent free radicals(EPFRs),pomelo peel(PP)and its physically divided portion,pomelo cuticle(PC),and white fiber(WF)were used as precursors to prepare six hydrochars:PPH-Fe,PCH-Fe,WFH-Fe,PPH,PCH,and WFH with and without Fe(III)addition during hydrothermal carbonization(HTC).PPH-Fe and WFH-Fe had higher EPFRs content(9.11×10^(18)and 8.25×10^(18)spins·g^(−1))compared to PPH and WFH(3.33×10^(18)and 2.96×10^(18)spins·g^(−1)),indicating that iron-doping favored EPFRs formation.However,PCH-Fe had lower EPFRs content(2.78×10^(18)spins·g^(−1))than PCH(7.95×10^(18)spins·g^(−1)),possibly due to excessive iron leading to the consumption of the generated EPFRs.For another reason,the required Fe(III)amount for EPFRs formation might vary among different precursors.PC has a lower concentration of phenolic compounds but 68-97%fatty acids,while WF and PP are rich in cellulose and lignin.In the Fenton-like reaction,oxygen-centered radicals of hydrochar played a significant role in activating H_(2)O_(2)and efficiently degrading bisphenol A(BPA).Mechanisms of reactive oxygen species(ROS)generation in hydrochar/H_(2)O_(2)system were proposed.EPFRs on hydrochar activate H_(2)O_(2)via electron transfer,creating·OH and 1O2,leading to BPA degradation.More importantly,the embedded EPFRs on the hydrochar’s inner surface contributed to the prolonged Fenton-like reactivity of PPH-Fe stored for 45 days.This study demonstrates that by optimizing precursor selection and iron doping,hydrochars can be engineered to maximize their EPFRs content and reactivity,providing a cost-effective solution for the degradation of hazardous pollutants.
