The abatements of 89 pharmaceuticals in secondary effluent by ozonation and the electro-peroxone(E-peroxone)process were investigated.Based on the results,a quantitative structure-activity relationship(QSAR)model was ...The abatements of 89 pharmaceuticals in secondary effluent by ozonation and the electro-peroxone(E-peroxone)process were investigated.Based on the results,a quantitative structure-activity relationship(QSAR)model was developed to explore relationship between chemical structure of pharmaceuticals and their oxidation rates by ozone.The orthogonal projection to latent structure(OPLS)method was used to identify relevant chemical descriptors of the pharmaceuticals,from large number of descriptors,for model development.The resulting QSAR model,based on 44 molecular descriptors related to the ozone reactivity of the pharmaceuticals,showed high goodness of fit(R^(2)=0.963)and predictive power(Q^(2)=0.84).After validation,the model was used to predict second-order rate constants of 491 pharmaceuticals of special concern(k_(O_(3)))including the 89 studied experimentally.The predicted k_(O_(3))values and experimentally determined pseudo-first order rate constants of the pharmaceuticals’abatement during ozonation(k_(OZ))and the E-peroxone process(k_(EP))were then used to assess effects of switching from ozonation to the E-peroxone process on removal of these pharmaceuticals.The results indicate that the E-peroxone process could accelerate the abatement of pharmaceuticals with relatively low ozone reactivity(k_(O_(3))<∼10^(2)M^(−1)⋅s^(−1))than ozonation(3–10 min versus 5–20 min).The validated QSAR model predicted 66 pharmaceuticals to be highly O_(3)-resistant.The developed QSAR model may be used to estimate the ozone reactivity of pharmaceuticals of diverse chemistry and thus predict their fate in ozone-based processes.展开更多
Halomethoxybenzenes(HMBs)are a group of compounds with natural and anthropogenic origins.Here we extend a 2002e2015 survey of bromoanisoles(BAs)in the air and precipitation at Rå€o on the Swedish west coast and P...Halomethoxybenzenes(HMBs)are a group of compounds with natural and anthropogenic origins.Here we extend a 2002e2015 survey of bromoanisoles(BAs)in the air and precipitation at Rå€o on the Swedish west coast and Pallas in Subarctic Finland.New BAs data are reported for 2018 and 2019 and chlorinated HMBs are included for these and some previous years:drosophilin A methyl ether(DAME:1,2,4,5-tetrachloro-3,6-dimethoxybenzene),tetrachloroveratrole(TeCV:1,2,3,4-tetrachloro-5,6-dimethoxybenzene),and pentachloroanisole(PeCA).The order of abundance of HMBs at Råo was SBAs>DAME>TeCV>PeCA,whereas at Pallas the order of abundance was DAME>SBAs>TeCA>PeCA.The lower abundance of BAs at Pallas reflects its inland location,away from direct marine influence.Clausius-Clapeyron(CC)plots of log partial pressure(Pair)/Pa versus 1/T suggested distant transport at both sites for PeCA and local exchange for DAME and TeCV.BAs were dominated by distant transport at Pallas and by both local and distant sources at Rå€o.Relationships between air and precipitation concentrations were examined by scavenging ratios,SR=(ng m^(-3))precip/(ng m^(-3))air.SRs were higher at Pallas than Rå€o due to greater Henry's law partitioning of gaseous compounds into precipitation at colder temperatures.DAME is produced by terrestrial fungi.We screened 19 fungal species from Swedish forests and found seven of them contained 0.01e3.8 mg DAME per kg fresh weight.We suggest that the volatilization of DAME from fungi and forest litter containing fungal mycelia may contribute to atmospheric levels at both sites.展开更多
Halogenated natural products(HNPs)are organic compounds containing bromine,chlorine,iodine,and rarely fluorine.HNPs comprise many classes of compounds,ranging in complexity from halocarbons to higher molecular weight ...Halogenated natural products(HNPs)are organic compounds containing bromine,chlorine,iodine,and rarely fluorine.HNPs comprise many classes of compounds,ranging in complexity from halocarbons to higher molecular weight compounds,which often contain oxygen and/or nitrogen atoms in addition to halogens.Many HNPs are biosynthesized by marine bacteria,macroalgae,phytoplankton,tunicates,corals,worms,sponges and other invertebrates.This paper reviews HNPs in Arctic,Subarctic and Nordic ecosystems and is based on sections of Chapter 2.16 in the Arctic Monitoring and Assessment Program(AMAP)assessment Chemicals of Emerging Arctic Concern(AMAP,2017)which deal with the higher molecular weight HNPs.Material is updated and expanded to include more Nordic examples.Much of the chapter is devoted to“bromophenolic”HNPs,viz bromophenols(BPs)and transformation products bromoanisoles(BAs),hydroxylated and methoxylated bromodiphenyl ethers(OH-BDEs,MeO-BDEs)and polybrominated dibenzo-p-dioxins(PBDDs),since these HNPs are most frequently reported.Others discussed are 2,20-dimethoxy-3,30,5,50-tetrabromobiphenyl(2,20-dimethoxy-BB80),polyhalogenated 10-methyl-1,20-bipyrroles(PMBPs),polyhalogenated 1,10-dimethyl-2,20-bipyrroles(PDBPs),polyhalogenated N-methylpyrroles(PMPs),polyhalogenated N-methylindoles(PMIs),bromoheptyl-and bromooctyl pyrroles,(1R,2S,4R,5R,10E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(20-chloroethenyl)-5-methylcyclohexane(mixed halogenated compound MHC-1),polybrominated hexahydroxanthene derivatives(PBHDs)and polyhalogenated carbazoles(PHCs).Aspects of HNPs covered are physicochemical properties,sources and production,transformation processes,concentrations and trends in the physical environment and biota(marine and freshwater).Toxic properties of some HNPs and a discussion of how climate change might affect HNPs production and distribution are also included.The review concludes with a summary of research needs to better understand the role of HNPs as“chemicals of emerging Arctic concern”.展开更多
基金the NSFC(Grant No.51878370)the National Special Program of Water Pollution Control and Management(2017ZX07202)the special fund of State Key Joint Laboratory of Environment Simulation and Pollution Control(18L01ESPC).
文摘The abatements of 89 pharmaceuticals in secondary effluent by ozonation and the electro-peroxone(E-peroxone)process were investigated.Based on the results,a quantitative structure-activity relationship(QSAR)model was developed to explore relationship between chemical structure of pharmaceuticals and their oxidation rates by ozone.The orthogonal projection to latent structure(OPLS)method was used to identify relevant chemical descriptors of the pharmaceuticals,from large number of descriptors,for model development.The resulting QSAR model,based on 44 molecular descriptors related to the ozone reactivity of the pharmaceuticals,showed high goodness of fit(R^(2)=0.963)and predictive power(Q^(2)=0.84).After validation,the model was used to predict second-order rate constants of 491 pharmaceuticals of special concern(k_(O_(3)))including the 89 studied experimentally.The predicted k_(O_(3))values and experimentally determined pseudo-first order rate constants of the pharmaceuticals’abatement during ozonation(k_(OZ))and the E-peroxone process(k_(EP))were then used to assess effects of switching from ozonation to the E-peroxone process on removal of these pharmaceuticals.The results indicate that the E-peroxone process could accelerate the abatement of pharmaceuticals with relatively low ozone reactivity(k_(O_(3))<∼10^(2)M^(−1)⋅s^(−1))than ozonation(3–10 min versus 5–20 min).The validated QSAR model predicted 66 pharmaceuticals to be highly O_(3)-resistant.The developed QSAR model may be used to estimate the ozone reactivity of pharmaceuticals of diverse chemistry and thus predict their fate in ozone-based processes.
文摘Halomethoxybenzenes(HMBs)are a group of compounds with natural and anthropogenic origins.Here we extend a 2002e2015 survey of bromoanisoles(BAs)in the air and precipitation at Rå€o on the Swedish west coast and Pallas in Subarctic Finland.New BAs data are reported for 2018 and 2019 and chlorinated HMBs are included for these and some previous years:drosophilin A methyl ether(DAME:1,2,4,5-tetrachloro-3,6-dimethoxybenzene),tetrachloroveratrole(TeCV:1,2,3,4-tetrachloro-5,6-dimethoxybenzene),and pentachloroanisole(PeCA).The order of abundance of HMBs at Råo was SBAs>DAME>TeCV>PeCA,whereas at Pallas the order of abundance was DAME>SBAs>TeCA>PeCA.The lower abundance of BAs at Pallas reflects its inland location,away from direct marine influence.Clausius-Clapeyron(CC)plots of log partial pressure(Pair)/Pa versus 1/T suggested distant transport at both sites for PeCA and local exchange for DAME and TeCV.BAs were dominated by distant transport at Pallas and by both local and distant sources at Rå€o.Relationships between air and precipitation concentrations were examined by scavenging ratios,SR=(ng m^(-3))precip/(ng m^(-3))air.SRs were higher at Pallas than Rå€o due to greater Henry's law partitioning of gaseous compounds into precipitation at colder temperatures.DAME is produced by terrestrial fungi.We screened 19 fungal species from Swedish forests and found seven of them contained 0.01e3.8 mg DAME per kg fresh weight.We suggest that the volatilization of DAME from fungi and forest litter containing fungal mycelia may contribute to atmospheric levels at both sites.
基金Support to TFB was provided by the Swedish Research Environment EcoChange.LMJ acknowledges support for an exchange visit to UmeåUniversity from ARCUM,the Arctic Research Institute at UmeåUniversity.Disclaimer:Certain commercial equipment or instruments are identified in the paper to specify adequately the experimental procedures.Such identification does not imply recommendations or endorsement by the National Institute of Standards and Technologynor does it imply that the equipment or instruments are the best available for the purpose.Any use of trade,firm,or product names is for descriptive purposes only and does not constitute endorsement by the U.S.Government.
文摘Halogenated natural products(HNPs)are organic compounds containing bromine,chlorine,iodine,and rarely fluorine.HNPs comprise many classes of compounds,ranging in complexity from halocarbons to higher molecular weight compounds,which often contain oxygen and/or nitrogen atoms in addition to halogens.Many HNPs are biosynthesized by marine bacteria,macroalgae,phytoplankton,tunicates,corals,worms,sponges and other invertebrates.This paper reviews HNPs in Arctic,Subarctic and Nordic ecosystems and is based on sections of Chapter 2.16 in the Arctic Monitoring and Assessment Program(AMAP)assessment Chemicals of Emerging Arctic Concern(AMAP,2017)which deal with the higher molecular weight HNPs.Material is updated and expanded to include more Nordic examples.Much of the chapter is devoted to“bromophenolic”HNPs,viz bromophenols(BPs)and transformation products bromoanisoles(BAs),hydroxylated and methoxylated bromodiphenyl ethers(OH-BDEs,MeO-BDEs)and polybrominated dibenzo-p-dioxins(PBDDs),since these HNPs are most frequently reported.Others discussed are 2,20-dimethoxy-3,30,5,50-tetrabromobiphenyl(2,20-dimethoxy-BB80),polyhalogenated 10-methyl-1,20-bipyrroles(PMBPs),polyhalogenated 1,10-dimethyl-2,20-bipyrroles(PDBPs),polyhalogenated N-methylpyrroles(PMPs),polyhalogenated N-methylindoles(PMIs),bromoheptyl-and bromooctyl pyrroles,(1R,2S,4R,5R,10E)-2-bromo-1-bromomethyl-1,4-dichloro-5-(20-chloroethenyl)-5-methylcyclohexane(mixed halogenated compound MHC-1),polybrominated hexahydroxanthene derivatives(PBHDs)and polyhalogenated carbazoles(PHCs).Aspects of HNPs covered are physicochemical properties,sources and production,transformation processes,concentrations and trends in the physical environment and biota(marine and freshwater).Toxic properties of some HNPs and a discussion of how climate change might affect HNPs production and distribution are also included.The review concludes with a summary of research needs to better understand the role of HNPs as“chemicals of emerging Arctic concern”.
