Low-carbon process for resource utilization of polycyclic aromatic hydrocarbons(PAHs)in zeolitecatalyzed processes,geared to carbon neutrality-a prominent trend throughout human activities,has been bottlenecked by the...Low-carbon process for resource utilization of polycyclic aromatic hydrocarbons(PAHs)in zeolitecatalyzed processes,geared to carbon neutrality-a prominent trend throughout human activities,has been bottlenecked by the lack of a complete mechanistic understanding of coking and decoking chemistry,involving the speciation and molecular evolution of PAHs,the plethora of which causes catalyst deactivation and forces regeneration,rendering significant CO_(2) emission.Herein,by exploiting the high-resolution matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry(MALDI FT-ICR MS),we unveil the missing fingerprints of the mechanistic pathways for both formation and decomposition of cross-linked cage-passing PAHs for SAPO-34-catalyzed,industrially relevant methanol-to-olefins(MTO)as a model reaction.Notable is the molecule-resolved symmetrical signature:their speciation originates exclusively from the direct coupling of in-cage hydrocarbon pool(HCP)species,whereas water-promoted decomposition of cage-passing PAHs initiates with selective cracking of inter-cage local structures at 8-rings followed by deep aromatic steam reforming.Molecular deciphering the reversibly dynamic evolution trajectory(fate)of full-spectrum aromatic hydrocarbons and fulfilling the real-time quantitative carbon resource footprints advance the fundamental knowledge of deactivation and regeneration phenomena(decay and recovery motifs of autocatalysis)and disclose the underlying mechanisms of especially the chemistry of coking and decoking in zeolite catalysis.The positive yet divergent roles of water in these two processes are disentangled.These unprecedented insights ultimately lead us to a steam regeneration strategy with valuable CO and H_(2) as main products,negligible CO_(2) emission in steam reforming and full catalyst activity recovery,which further proves feasible in other important chemical processes,promising to be a sustainable and potent approach that contributes to carbon-neutral chemical industry.展开更多
In the present work, the different sample collection, pretreatment and analytical methods for polycyclic aromatic hydrocarbons （PAHs） in airborne particulates is systematacially reviewed, and the applications of the...In the present work, the different sample collection, pretreatment and analytical methods for polycyclic aromatic hydrocarbons （PAHs） in airborne particulates is systematacially reviewed, and the applications of these pretreatment and analytical methods for PAHs are compared in detail. Some comments on the future expectation are also presented.展开更多
Sensitivity is crucially important for surface-enhanced Raman spectroscopy(SERS)application to detect trace-level polycyclic aromatic hydrocarbons(PAHs)in the seawater.In this study,a high sensitivity three-dimensiona...Sensitivity is crucially important for surface-enhanced Raman spectroscopy(SERS)application to detect trace-level polycyclic aromatic hydrocarbons(PAHs)in the seawater.In this study,a high sensitivity three-dimensional(3-D)SERS substrate composed with syringe filter,glycidyl methacrylate-ethylene dimethacrylate(GMA-EDMA)porous material and optimal parameters(57 nm,pH 13)gold nanoparticles(Au NPs)was developed for the detection of PAHs in water.The enhancement effect and repeatability of this 3-D substrate were also explored.The Raman intensity of pyrene using 3-D SERS substrate is about 8 times higher than that of substrate only using p H 13 gold colloid solution and about 12 times higher than that of substrate using natural Au NPs and GMA-EDMA porous material,which means both the pH 13 AuN Ps and the GMA-EDMA porous material are important factors for the sensitivity of this 3-D SERS substrate.Good repeatability of this optimal 3-D substrate was obtained.The relative standard deviation(RSD)is less than 8.66% on the same substrate and less than 3.69% on other different substrates.Four kinds of PAHs,i.e.,phenanthrene,pyrene,benzo(a)pyrene,benzo(k)fluoranthene and their mixture,were detected at the different concentrations.Their limits of detection(LODs)are 8.3×10^-10(phenanthrene),2.1×10^-10(pyrene),3.8×10^-10(benzo(a)pyrene)and 1.7×10^-10 mol L^-1(benzo(k)fluoranthene),respectively.In addition,these four PAHs were also detected by fluorescence spectroscopy to evaluate the sensitivity of SERS technology using this optimal 3-D SERS substrate.The results showed that the sensitivity of SERS based on the 3-D SERS substrate even using the portable Raman system was closed to that of fluorescence spectroscopy.Therefore,the SERS technology using this optimal 3-D substrate is expected to be an in-situ method for the detection of environmental PAHs.展开更多
This research aims to investigate the pollution characteristic of PAHs in Xiaodian sewage irrigation area. The result shows that the concentrations ofPAHs range from 47.94 to 46432.85ng/g while that of the total compo...This research aims to investigate the pollution characteristic of PAHs in Xiaodian sewage irrigation area. The result shows that the concentrations ofPAHs range from 47.94 to 46432.85ng/g while that of the total components of the 16 kinds of PAHs are 5969.81ng/g. PAHs with for rings and more than 4 rings are the main and important pollutants in topsoils of Xiaodian District. The main input of PAHs is combustion source, and the main pollution source in this area is fired coal. The topsoils in Xiaodian District are polluted by human activity in varying degrees. 23 of all 31 topsoil samples have been heavily polluted, especially those located nearby developed industrial townships and irrigation channels.展开更多
The present study was used freshwater Crab （Sesarma boulengeri Caiman） as bioindicator to measured the PAHs levels in AI-Hilla River, Iraq, during the period from March 2010 to February 2011. Crab samples were colle...The present study was used freshwater Crab （Sesarma boulengeri Caiman） as bioindicator to measured the PAHs levels in AI-Hilla River, Iraq, during the period from March 2010 to February 2011. Crab samples were collected from two sites on the AI-Hilla River. Sixteen of PAils compounds were identified seasonally in these samples. High mean value was （72.06 μg/g）, recorded by Dibenzo （a, h） anthracene （DbA） in Site 1 and low mean value was （0.36 μg/g） recorded by Anthracene （Ant） in Site 2. The study showed a clear variation in PAHs concentration independent from the seasons and locations. Site 1 recorded high value of HMW （high molecular weight） and LMW （low molecular weight） more than Site 2. The present study revealed that all PAHs compounds were from Pyrogenic Origin. Seven carcinogenic PAHs （cPAHs） were recorded in crab tissues that were collected from the AI-Hilla River. The TEF （toxicity equivalency factor） was calculated to toxicity equivalent crab concentration. From the results, the fresh water Crab Sesarma boulengeri is a good bioindicator to water pollution by PAHs.展开更多
A new sampling method of ambient air analysis using carbonized fibrous resin as a sorbent for polycyclic aromatic hydrocarbons (PAHs) was reported. The physical and chemical properties of the carbonized fibrous resin...A new sampling method of ambient air analysis using carbonized fibrous resin as a sorbent for polycyclic aromatic hydrocarbons (PAHs) was reported. The physical and chemical properties of the carbonized fibrous resins were measured. The sample pretreatment with ultrasonic extraction and subsequent clean-up elution through a silica gel column was optimized. The suitable ultrasonic extraction conditions were selected as follows: resin weight was 1.5 g, ultrasonic extraction time 20 min, volume of extraction solvent 100 ml and extraction operation times 2~3. The concentrated extractable organic matter was submitted to next step of clean-up procedure of adsorption chromatography on silica gel column/n-hexane and a mixture of dichloromethene:n-hexane solution 2:3 (v/v). The PAHs fractions in the real samples from Changzhou, China were particularly analyzed using GC-MS data system and the data of mass spectra, retention times and scan numbers of the real samples were compared with that of the standards of 16 PAHs listed by the US EPA as 損riority pollutants?of the environment. The analysis of the real samples indicates that the carbonized fibrous resin is a good sorbent. The pretreatment of samples of ambient air with carbonized fibrous resin as a sorbent for PAHs is proved to be reliable and might be used for the procedure of the determination of PAHs in atmospheric environment.展开更多
Polycyclic aromatic hydrocarbons(PAHs)are one of the most important groups in oil,and re sponsible for major toxic and/or carcinogenic impact on humans and wildlife.It is important to understand the behavior of PAHs i...Polycyclic aromatic hydrocarbons(PAHs)are one of the most important groups in oil,and re sponsible for major toxic and/or carcinogenic impact on humans and wildlife.It is important to understand the behavior of PAHs in marine environment after an oil-spill incident.However,interaction between petroleum PAHs and microbial communities in a marine environment remains unclear.Therefore,a series of mesocosm experiments were conducted.in which water-accommodated fraction(WAF)of oil was generated to simulate an oil-spill scenario and to analyze the transport and behavior of marine oil spill containing PAHs with and without dispersants.Results indicate that the application of dispersant could increase the concentration of total PAHs in water column due mainly to significant increase in the concentration of highmolecular weight(HMW)PAHs at a lower removal rate.At the end of the 7-day experiment,significant amount of HMW PAHs were accumulated in sediment.In general,the application of dispersant did not increase the sediment uptake of PAHs but increased the PAHs concentration in water column.展开更多
基金financial support from the National Natural Science Foundation of China(21991092,21991090,22022202,21972142,21902153,21974138)the Chinese Academy of Sciences(QYZDY-SSW-SC024)the Dalian Institute of Chemical Physics(DICP I201926,DICP I201947)。
文摘Low-carbon process for resource utilization of polycyclic aromatic hydrocarbons(PAHs)in zeolitecatalyzed processes,geared to carbon neutrality-a prominent trend throughout human activities,has been bottlenecked by the lack of a complete mechanistic understanding of coking and decoking chemistry,involving the speciation and molecular evolution of PAHs,the plethora of which causes catalyst deactivation and forces regeneration,rendering significant CO_(2) emission.Herein,by exploiting the high-resolution matrix-assisted laser desorption/ionization Fourier-transform ion cyclotron resonance mass spectrometry(MALDI FT-ICR MS),we unveil the missing fingerprints of the mechanistic pathways for both formation and decomposition of cross-linked cage-passing PAHs for SAPO-34-catalyzed,industrially relevant methanol-to-olefins(MTO)as a model reaction.Notable is the molecule-resolved symmetrical signature:their speciation originates exclusively from the direct coupling of in-cage hydrocarbon pool(HCP)species,whereas water-promoted decomposition of cage-passing PAHs initiates with selective cracking of inter-cage local structures at 8-rings followed by deep aromatic steam reforming.Molecular deciphering the reversibly dynamic evolution trajectory(fate)of full-spectrum aromatic hydrocarbons and fulfilling the real-time quantitative carbon resource footprints advance the fundamental knowledge of deactivation and regeneration phenomena(decay and recovery motifs of autocatalysis)and disclose the underlying mechanisms of especially the chemistry of coking and decoking in zeolite catalysis.The positive yet divergent roles of water in these two processes are disentangled.These unprecedented insights ultimately lead us to a steam regeneration strategy with valuable CO and H_(2) as main products,negligible CO_(2) emission in steam reforming and full catalyst activity recovery,which further proves feasible in other important chemical processes,promising to be a sustainable and potent approach that contributes to carbon-neutral chemical industry.
基金Project supported by the National Natural Science Foundation of China (No. 20437020 20575073) NSFC-JSPS Joint Research Project (No. 20511140134) the Major Research Program of Chinese Academy of Sciences (KZCX3-SW-432)
文摘In the present work, the different sample collection, pretreatment and analytical methods for polycyclic aromatic hydrocarbons （PAHs） in airborne particulates is systematacially reviewed, and the applications of these pretreatment and analytical methods for PAHs are compared in detail. Some comments on the future expectation are also presented.
基金supported by the National Natural Science Foundation of China (No. 41476081)the Major Research and Development Project in Shandong Province (Nos. 2016GSF115020, 2019GHY112027)the Shandong Provincial Natural Science Foundation (No. ZR2015DM007)
文摘Sensitivity is crucially important for surface-enhanced Raman spectroscopy(SERS)application to detect trace-level polycyclic aromatic hydrocarbons(PAHs)in the seawater.In this study,a high sensitivity three-dimensional(3-D)SERS substrate composed with syringe filter,glycidyl methacrylate-ethylene dimethacrylate(GMA-EDMA)porous material and optimal parameters(57 nm,pH 13)gold nanoparticles(Au NPs)was developed for the detection of PAHs in water.The enhancement effect and repeatability of this 3-D substrate were also explored.The Raman intensity of pyrene using 3-D SERS substrate is about 8 times higher than that of substrate only using p H 13 gold colloid solution and about 12 times higher than that of substrate using natural Au NPs and GMA-EDMA porous material,which means both the pH 13 AuN Ps and the GMA-EDMA porous material are important factors for the sensitivity of this 3-D SERS substrate.Good repeatability of this optimal 3-D substrate was obtained.The relative standard deviation(RSD)is less than 8.66% on the same substrate and less than 3.69% on other different substrates.Four kinds of PAHs,i.e.,phenanthrene,pyrene,benzo(a)pyrene,benzo(k)fluoranthene and their mixture,were detected at the different concentrations.Their limits of detection(LODs)are 8.3×10^-10(phenanthrene),2.1×10^-10(pyrene),3.8×10^-10(benzo(a)pyrene)and 1.7×10^-10 mol L^-1(benzo(k)fluoranthene),respectively.In addition,these four PAHs were also detected by fluorescence spectroscopy to evaluate the sensitivity of SERS technology using this optimal 3-D SERS substrate.The results showed that the sensitivity of SERS based on the 3-D SERS substrate even using the portable Raman system was closed to that of fluorescence spectroscopy.Therefore,the SERS technology using this optimal 3-D substrate is expected to be an in-situ method for the detection of environmental PAHs.
文摘This research aims to investigate the pollution characteristic of PAHs in Xiaodian sewage irrigation area. The result shows that the concentrations ofPAHs range from 47.94 to 46432.85ng/g while that of the total components of the 16 kinds of PAHs are 5969.81ng/g. PAHs with for rings and more than 4 rings are the main and important pollutants in topsoils of Xiaodian District. The main input of PAHs is combustion source, and the main pollution source in this area is fired coal. The topsoils in Xiaodian District are polluted by human activity in varying degrees. 23 of all 31 topsoil samples have been heavily polluted, especially those located nearby developed industrial townships and irrigation channels.
文摘The present study was used freshwater Crab （Sesarma boulengeri Caiman） as bioindicator to measured the PAHs levels in AI-Hilla River, Iraq, during the period from March 2010 to February 2011. Crab samples were collected from two sites on the AI-Hilla River. Sixteen of PAils compounds were identified seasonally in these samples. High mean value was （72.06 μg/g）, recorded by Dibenzo （a, h） anthracene （DbA） in Site 1 and low mean value was （0.36 μg/g） recorded by Anthracene （Ant） in Site 2. The study showed a clear variation in PAHs concentration independent from the seasons and locations. Site 1 recorded high value of HMW （high molecular weight） and LMW （low molecular weight） more than Site 2. The present study revealed that all PAHs compounds were from Pyrogenic Origin. Seven carcinogenic PAHs （cPAHs） were recorded in crab tissues that were collected from the AI-Hilla River. The TEF （toxicity equivalency factor） was calculated to toxicity equivalent crab concentration. From the results, the fresh water Crab Sesarma boulengeri is a good bioindicator to water pollution by PAHs.
基金The Natural Science Foundation of Jangsu Province. No. BK93124313
文摘A new sampling method of ambient air analysis using carbonized fibrous resin as a sorbent for polycyclic aromatic hydrocarbons (PAHs) was reported. The physical and chemical properties of the carbonized fibrous resins were measured. The sample pretreatment with ultrasonic extraction and subsequent clean-up elution through a silica gel column was optimized. The suitable ultrasonic extraction conditions were selected as follows: resin weight was 1.5 g, ultrasonic extraction time 20 min, volume of extraction solvent 100 ml and extraction operation times 2~3. The concentrated extractable organic matter was submitted to next step of clean-up procedure of adsorption chromatography on silica gel column/n-hexane and a mixture of dichloromethene:n-hexane solution 2:3 (v/v). The PAHs fractions in the real samples from Changzhou, China were particularly analyzed using GC-MS data system and the data of mass spectra, retention times and scan numbers of the real samples were compared with that of the standards of 16 PAHs listed by the US EPA as 損riority pollutants?of the environment. The analysis of the real samples indicates that the carbonized fibrous resin is a good sorbent. The pretreatment of samples of ambient air with carbonized fibrous resin as a sorbent for PAHs is proved to be reliable and might be used for the procedure of the determination of PAHs in atmospheric environment.
文摘Polycyclic aromatic hydrocarbons(PAHs)are one of the most important groups in oil,and re sponsible for major toxic and/or carcinogenic impact on humans and wildlife.It is important to understand the behavior of PAHs in marine environment after an oil-spill incident.However,interaction between petroleum PAHs and microbial communities in a marine environment remains unclear.Therefore,a series of mesocosm experiments were conducted.in which water-accommodated fraction(WAF)of oil was generated to simulate an oil-spill scenario and to analyze the transport and behavior of marine oil spill containing PAHs with and without dispersants.Results indicate that the application of dispersant could increase the concentration of total PAHs in water column due mainly to significant increase in the concentration of highmolecular weight(HMW)PAHs at a lower removal rate.At the end of the 7-day experiment,significant amount of HMW PAHs were accumulated in sediment.In general,the application of dispersant did not increase the sediment uptake of PAHs but increased the PAHs concentration in water column.
