The migration of soil dissolved organic carbon(DOC) from terrestrial to aquatic environments has important impacts on the adjacent water quality and the transport of organic and inorganic contaminants.However,few stud...The migration of soil dissolved organic carbon(DOC) from terrestrial to aquatic environments has important impacts on the adjacent water quality and the transport of organic and inorganic contaminants.However,few studies have investigated the sources and properties of DOC in riparian zones.A total of 34 soil samples were collected across four riparian buffer zones(Zones A-D) on Chongming Island,China.The vertical distributions of soil organic carbon(SOC) and DOC,fluorescence excitation-emission matrix(EEM) spectra of DOC and the optical indices,including fluorescence index(FI),index of recent autochthonous contribution(BIX),and humification index(HIX),were measured across the riparian environment to investigate the sources and fluorescence properties of DOC.The results showed that SOC stored in the surface soil(0-30 cm) accounted for 40%of the total soil profile SOC.The DOC accumulated in Zones A-C,which accounted for 5%of the SOC.The fluorescence EEM spectra of DOC showed that DOC contained humic-like and protein-like substances,which were mainly derived from recent plant debris by microbes.A large amount of humic-like substances were sorbed to minerals in the surface soil(0-30 cm).In addition,the riparian topography and soil physico-chemical properties(pH,EC and moisture) dictated the transformation and transport of DOC.The results suggested that EEMs could reveal the source of DOC in riparian soil systems,and that optical indices were complementary tools that revealed the characteristics of soil DOC and provided supplemental evidence about DOC sources.展开更多
The membrane bioreactor(MBR)technology is a rising star for wastewater treatment.The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter(DOM)in the s...The membrane bioreactor(MBR)technology is a rising star for wastewater treatment.The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter(DOM)in the system.Three-dimensional excitation-emission matrix(3D-EEM)fluorescence spectroscopy,a powerful tool for the rapid and sensitive characterization of DOM,has been extensively applied in MBR studies;however,only a limited portion of the EEM fingerprinting information was utilized.This paper revisits the principles and methods of fluorescence EEM,and reviews the recent progress in applying EEM to characterize DOM in MBR studies.We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity,wavelength regional distribution,and spectral deconvolution(giving fluorescent component loadings/scores),and discussed how to use the information to interpret the chemical compositions,physiochemical properties,biological activities,membrane retention/fouling behaviors,and migration/transformation fates of DOM in MBR systems.In addition to conventional EEM indicators,novel fluorescent parameters are summarized for potential use,including quantum yield,Stokes shift,excited energy state,and fluorescence lifetime.The current limitations of EEM-based DOM characterization are also discussed,with possible measures proposed to improve applications in MBR monitoring.展开更多
Molecular weight（Mw） is a fundamental property of humic acids（HAs）, which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid（HA） extracted from Jin...Molecular weight（Mw） is a fundamental property of humic acids（HAs）, which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid（HA） extracted from Jinyun Mountain, Chongqing was ultra-filtered into four fractions according to the molecular weight, and their properties were characterized.Complexation of cadmium was investigated by titration experiments. For the first time,Langmuir and non-ideal competitive adsorption-Donna（NICA-Donnan） models combined with fluorescence excitation-emission matrix（EEM） quenching were employed to elucidate the binding characteristics of individual Mw fractions of HA. The results showed that the concentration of acidic functional groups decreased with increasing Mw, especially the phenolic groups. The humification degree and aliphaticity increased with increasing Mw as indicated by elemental composition analysis and FT-IR spectra. The binding capacity of Cd2＋ to Mw fractions of HA followed the order UF1（〈 5 kDa） 〉 UF2（5–10 kDa） 〉 UF4（〉 30 kDa） 〉 UF3（10–30 kDa）. Moreover, the distribution of cadmium speciation indicated that the phenolic groups were responsible for the variations in binding of Cd2＋ among different Mw fractions. The results of fluorescence quenching illustrated that the binding capacity of Cd2＋ to Mw fractions was controlled by the content of functional groups, while the binding affinity was largely influenced by structural factors. The results provide a better understanding of the roles that different HA Mw fractions play in heavy metal binding,which has important implications in the control of heavy metal migration and bio-toxicity.展开更多
Absorption and fluorescence properties of chromophoric dissolved organic matter （CDOM） along a 124 km transect in the Barataria Basin, a large estuary located in Louisiana, USA, were investigated during high and low...Absorption and fluorescence properties of chromophoric dissolved organic matter （CDOM） along a 124 km transect in the Barataria Basin, a large estuary located in Louisiana, USA, were investigated during high and low flow periods of the Mississippi River in the spring and winter of 2008-2009. Mean CDOM absorption at 355 nm from the marine to the freshwater end member stations ranged from （3.25 ± 0.56） to （20.76 ± 2.43） m^-1 for the three month high flow period whereas it varied from （1.48 ± 1.08） to （25.45 ± 7.03） m^-1 for the same stations during low flow period. Corresponding salinity values at these stations indicated the influence of river and shelf exchanges in the lower basin and precipitation and runoff in the upper basin. An inverse relationship of CDOM absorbance and fluorescence with salinity observed in the basin could he a useful indicator of salinity. CDOM fluorescence also varied over a large range showing an approximately 8 to 12-fold increase between the marine and freshwater end members for the two flow seasons. Excitation-emission matrix spectral plots indicated the presence of various fluorescence components with highest being the A-peak, lowest the T-peak, and the C and M-peaks showing similar trends along the transect. During low flow season the A/C ratio were well correlated with station locations indicating increased terrestrial influence towards the upper basin. CDOM absorption and fluorescence at 355 nm were highly correlated and independent of CDOM sources suggesting that fluorescence could be used to characterize CDOM in the basin.展开更多
To understand the aerosol characteristics in a regional background environment,fine-particle(PM_(2.5),n=228)samples were collected over a one-year period at the Shangdianzi(SDZ)station,which is a Global Atmospheric Wa...To understand the aerosol characteristics in a regional background environment,fine-particle(PM_(2.5),n=228)samples were collected over a one-year period at the Shangdianzi(SDZ)station,which is a Global Atmospheric Watch regional background station in North China.The chemical and optical characteristics of PM_(2.5)were analyzed,including organic carbon,elemental carbon,water-soluble organic carbon,water-soluble inorganic ions,and fluorescent components of watersoluble organic matter.The source factors of major aerosol components are apportioned,and the sources of the fluorescent chromophores are further analyzed.The major chemical components of PM_(2.5)at SDZ were NO_(3)^(-),organic matter,SO_(4)^(2-),and NH_(4)^(+).Annually,water-soluble organic carbon contributed 48%±15%to the total organic carbon.Secondary formation(52%)and fossil fuel combustion(63%)are the largest sources of water-soluble organic matter and water-insoluble organic matter,respectively.In addition,three humic-like and one protein-like matter were identified via parallel factor analysis for excitation–emission matrices.The fluorescence intensities of the components were highest in winter and lowest in summer,indicating the main impact of burning sources.This study contributes to understanding the chemical and optical characteristics of ambient aerosols in the background atmosphere.展开更多
The feasibility of using fluorescence excitation-emission matrix(EEM) along with parallel factor analysis(PARAFAC) and nonnegative least squares(NNLS) method for the differentiation of phytoplankton taxonomic groups w...The feasibility of using fluorescence excitation-emission matrix(EEM) along with parallel factor analysis(PARAFAC) and nonnegative least squares(NNLS) method for the differentiation of phytoplankton taxonomic groups was investigated. Forty-one phytoplankton species belonging to 28 genera of five divisions were studied. First, the PARAFAC model was applied to EEMs, and 15 fluorescence components were generated. Second, 15 fluorescence components were found to have a strong discriminating capability based on Bayesian discriminant analysis(BDA). Third, all spectra of the fluorescence component compositions for the 41 phytoplankton species were spectrographically sorted into 61 reference spectra using hierarchical cluster analysis(HCA), and then, the reference spectra were used to establish a database. Finally, the phytoplankton taxonomic groups was differentiated by the reference spectra database using the NNLS method. The five phytoplankton groups were differentiated with the correct discrimination ratios(CDRs) of 100% for single-species samples at the division level. The CDRs for the mixtures were above 91% for the dominant phytoplankton species and above 73% for the subdominant phytoplankton species. Sixteen of the 85 field samples collected from the Changjiang River estuary were analyzed by both HPLC-CHEMTAX and the fluorometric technique developed. The results of both methods reveal that Bacillariophyta was the dominant algal group in these 16 samples and that the subdominant algal groups comprised Dinophyta, Chlorophyta and Cryptophyta. The differentiation results by the fluorometric technique were in good agreement with those from HPLC-CHEMTAX. The results indicate that the fluorometric technique could differentiate algal taxonomic groups accurately at the division level.展开更多
To better understand the role of organic matter(OM)prepared from chicken manure and agriculture residues compost on the growth of plants(Lepidium sativum L.)and antagonistic fungi(Trichoderma harzianum),we analyzed th...To better understand the role of organic matter(OM)prepared from chicken manure and agriculture residues compost on the growth of plants(Lepidium sativum L.)and antagonistic fungi(Trichoderma harzianum),we analyzed the structure and composition of extracted OM using fluorescence excitation-emission matrix(EEM)spectroscopy and solid-state13C cross-polarization magic-anglespinning nuclear magnetic resonance(13C CPMAS NMR)spectroscopy.The results showed that the EEM contours of water-extracted OM(WEOM)and alkali-extracted OM(AEOM)were similar.Furthermore,solid-state13C CPMAS NMR spectroscopy demonstrated that water extraction could not proportionally pull out aromatic moieties(112–145 ppm)from compost,but the alkali method in proportion extracted both carbohydrates(65–85 ppm)and aromatic moieties.The results suggest that AEOM may better reflect the bulk OM composition of compost,and one should be cautious when applying WEOM as an alternative indicator of total compost OM.Further investigations demonstrated that,compared to carbohydrates,aromatic moieties played a predominant role in growth suppression of Lepidium sativum L.seeds and Trichoderma harzianum.展开更多
基金supported by the Major Science and Technology Program for Water Pollution Control and Treatment of China(Nos.2011ZX07303-001 and 2014ZX07303-003)the State Key Laboratory of Soil and Sustainable Agriculture,Institute of Soil Science,Chinese Academy of Sciences(No.Y412201426)
文摘The migration of soil dissolved organic carbon(DOC) from terrestrial to aquatic environments has important impacts on the adjacent water quality and the transport of organic and inorganic contaminants.However,few studies have investigated the sources and properties of DOC in riparian zones.A total of 34 soil samples were collected across four riparian buffer zones(Zones A-D) on Chongming Island,China.The vertical distributions of soil organic carbon(SOC) and DOC,fluorescence excitation-emission matrix(EEM) spectra of DOC and the optical indices,including fluorescence index(FI),index of recent autochthonous contribution(BIX),and humification index(HIX),were measured across the riparian environment to investigate the sources and fluorescence properties of DOC.The results showed that SOC stored in the surface soil(0-30 cm) accounted for 40%of the total soil profile SOC.The DOC accumulated in Zones A-C,which accounted for 5%of the SOC.The fluorescence EEM spectra of DOC showed that DOC contained humic-like and protein-like substances,which were mainly derived from recent plant debris by microbes.A large amount of humic-like substances were sorbed to minerals in the surface soil(0-30 cm).In addition,the riparian topography and soil physico-chemical properties(pH,EC and moisture) dictated the transformation and transport of DOC.The results suggested that EEMs could reveal the source of DOC in riparian soil systems,and that optical indices were complementary tools that revealed the characteristics of soil DOC and provided supplemental evidence about DOC sources.
基金the National Natural Science Foundation of China(No.51778599)the Beijing Natural Science Foundation(No.LI82044)+1 种基金the CAS Strategic Priority Research Programmer(A)(No.XDA20050103)the Youth Innovation Promotion Association CAS(No.110500EA62)。
文摘The membrane bioreactor(MBR)technology is a rising star for wastewater treatment.The pollutant elimination and membrane fouling performances of MBRs are essentially related to the dissolved organic matter(DOM)in the system.Three-dimensional excitation-emission matrix(3D-EEM)fluorescence spectroscopy,a powerful tool for the rapid and sensitive characterization of DOM,has been extensively applied in MBR studies;however,only a limited portion of the EEM fingerprinting information was utilized.This paper revisits the principles and methods of fluorescence EEM,and reviews the recent progress in applying EEM to characterize DOM in MBR studies.We systematically introduced the information extracted from EEM by considering the fluorescence peak location/intensity,wavelength regional distribution,and spectral deconvolution(giving fluorescent component loadings/scores),and discussed how to use the information to interpret the chemical compositions,physiochemical properties,biological activities,membrane retention/fouling behaviors,and migration/transformation fates of DOM in MBR systems.In addition to conventional EEM indicators,novel fluorescent parameters are summarized for potential use,including quantum yield,Stokes shift,excited energy state,and fluorescence lifetime.The current limitations of EEM-based DOM characterization are also discussed,with possible measures proposed to improve applications in MBR monitoring.
基金supported by the National Natural Science Foundation of China(Nos.41771347 and 4177010514)
文摘Molecular weight（Mw） is a fundamental property of humic acids（HAs）, which considerably affect the mobility and speciation of heavy metals in the environment. In this study, soil humic acid（HA） extracted from Jinyun Mountain, Chongqing was ultra-filtered into four fractions according to the molecular weight, and their properties were characterized.Complexation of cadmium was investigated by titration experiments. For the first time,Langmuir and non-ideal competitive adsorption-Donna（NICA-Donnan） models combined with fluorescence excitation-emission matrix（EEM） quenching were employed to elucidate the binding characteristics of individual Mw fractions of HA. The results showed that the concentration of acidic functional groups decreased with increasing Mw, especially the phenolic groups. The humification degree and aliphaticity increased with increasing Mw as indicated by elemental composition analysis and FT-IR spectra. The binding capacity of Cd2＋ to Mw fractions of HA followed the order UF1（〈 5 kDa） 〉 UF2（5–10 kDa） 〉 UF4（〉 30 kDa） 〉 UF3（10–30 kDa）. Moreover, the distribution of cadmium speciation indicated that the phenolic groups were responsible for the variations in binding of Cd2＋ among different Mw fractions. The results of fluorescence quenching illustrated that the binding capacity of Cd2＋ to Mw fractions was controlled by the content of functional groups, while the binding affinity was largely influenced by structural factors. The results provide a better understanding of the roles that different HA Mw fractions play in heavy metal binding,which has important implications in the control of heavy metal migration and bio-toxicity.
基金support provided by the Minerals Management Service (MMS)-Coastal Marine Institute (CMI) Cooperative Agreement (1435- 0104CA32806)a NASA grant (No. NNA07CN12A) to E. D'Saa Northern Gulf of Mexico Initiative (NGI)-Shell grant
文摘Absorption and fluorescence properties of chromophoric dissolved organic matter （CDOM） along a 124 km transect in the Barataria Basin, a large estuary located in Louisiana, USA, were investigated during high and low flow periods of the Mississippi River in the spring and winter of 2008-2009. Mean CDOM absorption at 355 nm from the marine to the freshwater end member stations ranged from （3.25 ± 0.56） to （20.76 ± 2.43） m^-1 for the three month high flow period whereas it varied from （1.48 ± 1.08） to （25.45 ± 7.03） m^-1 for the same stations during low flow period. Corresponding salinity values at these stations indicated the influence of river and shelf exchanges in the lower basin and precipitation and runoff in the upper basin. An inverse relationship of CDOM absorbance and fluorescence with salinity observed in the basin could he a useful indicator of salinity. CDOM fluorescence also varied over a large range showing an approximately 8 to 12-fold increase between the marine and freshwater end members for the two flow seasons. Excitation-emission matrix spectral plots indicated the presence of various fluorescence components with highest being the A-peak, lowest the T-peak, and the C and M-peaks showing similar trends along the transect. During low flow season the A/C ratio were well correlated with station locations indicating increased terrestrial influence towards the upper basin. CDOM absorption and fluorescence at 355 nm were highly correlated and independent of CDOM sources suggesting that fluorescence could be used to characterize CDOM in the basin.
基金supported by the National Natural Science Foundation of China(Grant Nos.42130513 and 41625014)the National Key Research and Development Program of China(Grant No.2019YFA0606801)。
文摘To understand the aerosol characteristics in a regional background environment,fine-particle(PM_(2.5),n=228)samples were collected over a one-year period at the Shangdianzi(SDZ)station,which is a Global Atmospheric Watch regional background station in North China.The chemical and optical characteristics of PM_(2.5)were analyzed,including organic carbon,elemental carbon,water-soluble organic carbon,water-soluble inorganic ions,and fluorescent components of watersoluble organic matter.The source factors of major aerosol components are apportioned,and the sources of the fluorescent chromophores are further analyzed.The major chemical components of PM_(2.5)at SDZ were NO_(3)^(-),organic matter,SO_(4)^(2-),and NH_(4)^(+).Annually,water-soluble organic carbon contributed 48%±15%to the total organic carbon.Secondary formation(52%)and fossil fuel combustion(63%)are the largest sources of water-soluble organic matter and water-insoluble organic matter,respectively.In addition,three humic-like and one protein-like matter were identified via parallel factor analysis for excitation–emission matrices.The fluorescence intensities of the components were highest in winter and lowest in summer,indicating the main impact of burning sources.This study contributes to understanding the chemical and optical characteristics of ambient aerosols in the background atmosphere.
基金Supported by the National Natural Science Foundation of China(Nos.41376106,41176063)the Shandong Provincial Natural Science Foundation of China(No.ZR2013DM017)
文摘The feasibility of using fluorescence excitation-emission matrix(EEM) along with parallel factor analysis(PARAFAC) and nonnegative least squares(NNLS) method for the differentiation of phytoplankton taxonomic groups was investigated. Forty-one phytoplankton species belonging to 28 genera of five divisions were studied. First, the PARAFAC model was applied to EEMs, and 15 fluorescence components were generated. Second, 15 fluorescence components were found to have a strong discriminating capability based on Bayesian discriminant analysis(BDA). Third, all spectra of the fluorescence component compositions for the 41 phytoplankton species were spectrographically sorted into 61 reference spectra using hierarchical cluster analysis(HCA), and then, the reference spectra were used to establish a database. Finally, the phytoplankton taxonomic groups was differentiated by the reference spectra database using the NNLS method. The five phytoplankton groups were differentiated with the correct discrimination ratios(CDRs) of 100% for single-species samples at the division level. The CDRs for the mixtures were above 91% for the dominant phytoplankton species and above 73% for the subdominant phytoplankton species. Sixteen of the 85 field samples collected from the Changjiang River estuary were analyzed by both HPLC-CHEMTAX and the fluorometric technique developed. The results of both methods reveal that Bacillariophyta was the dominant algal group in these 16 samples and that the subdominant algal groups comprised Dinophyta, Chlorophyta and Cryptophyta. The differentiation results by the fluorometric technique were in good agreement with those from HPLC-CHEMTAX. The results indicate that the fluorometric technique could differentiate algal taxonomic groups accurately at the division level.
基金Supported by the National Basic Research Program(973 Program)of China(No.2011CB100503)the National Natural Science Foundation of China(No.21007027)+1 种基金the Qing Lan Project of Jiangsu Province,Chinathe National"111"Project of China’s Higher Education(No.B12009)
文摘To better understand the role of organic matter(OM)prepared from chicken manure and agriculture residues compost on the growth of plants(Lepidium sativum L.)and antagonistic fungi(Trichoderma harzianum),we analyzed the structure and composition of extracted OM using fluorescence excitation-emission matrix(EEM)spectroscopy and solid-state13C cross-polarization magic-anglespinning nuclear magnetic resonance(13C CPMAS NMR)spectroscopy.The results showed that the EEM contours of water-extracted OM(WEOM)and alkali-extracted OM(AEOM)were similar.Furthermore,solid-state13C CPMAS NMR spectroscopy demonstrated that water extraction could not proportionally pull out aromatic moieties(112–145 ppm)from compost,but the alkali method in proportion extracted both carbohydrates(65–85 ppm)and aromatic moieties.The results suggest that AEOM may better reflect the bulk OM composition of compost,and one should be cautious when applying WEOM as an alternative indicator of total compost OM.Further investigations demonstrated that,compared to carbohydrates,aromatic moieties played a predominant role in growth suppression of Lepidium sativum L.seeds and Trichoderma harzianum.
