Characterization of chromophoric dissolved organic matter(CDOM) in the East China Sea in autumn using excitationemission matrix(EEM) fluorescence and parallel factor analysis(PARAFAC)

Samples of chromophoric dissolved organic matter （CDOM） in the East China Sea in autumn （October in 2011） were analyzed by excitation emission matrix （EEM） fluorescence spectroscopy combined with parallel factor analysis （PARAFAC）. Three terrestrial humic-like components （C1, C2 and C3） and one protein-like component （C4） were identified. Based on spatial dis- tributions, as well as relationships with salinity, the following assignments were made. The three humic-like components （CI, C2 and C3） showed conservative mixing behavior and came mainly from riverine input. The protein-like component （C4） was considered a combination of autochthonous production and terrestrial inputs and a biologically labile component. Path analysis of samples from the middle and bottom layers revealed that the causal effects on C1 were -78.46% for salinity, and -21.54% for apparent oxygen utilization （AOU）; those on C2 were -76.43% for salinity, and -23.57% for AOU; those on C3 were -70.49% for salinity, 7.01% for Chl-a, and -22.50% for AOU; those on C4 were -55.54% for salinity, 14.6% for Chl-a, and -29.86% for AOU in middle layer; and those on C4 were -57.37% for salinity, 29.02% for Chl-a, and -13.61% for AOU in bottom layer. Results indicated that CDOM in tile East China Sea was mainly affected by terrestrial inputs, and microbial ac- tivities also played a key role in biogeochemical processes of CDOM. The application of the EEM-PARAFAC model present- ed a unique opportunity to observe compositional changes in CDOM in the East China Sea. In addition, the humification index （HIX） suggested that CDOM from the East China Sea was less stable and stayed shorter in the environment.

Rapid and simple analysis of amphetamine-type illegal drugs using excitation–emission matrix fluorescence coupled with parallel factor analysis

Nowadays,the abuse of illegal drugs has been an increasingly grim problem in the world.Excitation–emission matrix fluorescence combined with parallel factor analysis was used to make a quantitative analysis of the simulated amphetamine-type illegal drugs.Satisfactory results were achieved for simultaneous determination of methamphetamine(MAM)and 3,4-methylenedioxymethamphetamine(MDMA)in the presence of adulterants.The average recoveries were(99.8±0.6)%and(101.6±5.7)%for MAM and MDMA,respectively.Figures of merit including root-mean-square error of calibration and prediction,sensitivity and selectivity were investigated to evaluate the performance of the proposed method.The limits of detection were 0.054 and 0.0021 g/mL for MAM and MDMA,respectively.

Characteristics of extracellular fluorescent substances of aerobic granular sludge in pilot-scale sequencing batch reactor

The aerobic granular sludge was cultivated in a pilot-scale sequencing batch reactor （SBR）, and some of the granules were stored at 8 ℃ for 150 d. Extracellular polymeric substances （EPS） of sludge samples were extracted and analyzed during the granulation and storage process. The results show that the contents of protein and EPS increase along with the granulation process, while polysaccharides remain almost unchanged. The content of protein in EPS is almost two-fold larger than that of polysaccharides in granular sludge cultivated with municipal wastewater. Moreover, some of the granules disintegrate during storage, corresponding to the decrease of protein contents in EPS. Three peaks are identified in three-dimensional excitation emission matrix （EEM） fluorescence spectra of the EPS in the aerobic granules. Two peaks （A and B） are attributed to the protein-like fluorophores, and the third （peak C） is related to visible fulvic-like substances. Peak A gradually disappears during storage, while a new peak related to ultraviolet fulvic acid （peak D） is formed. The formation and the stability of aerobic granules are closely dependent on the quantity and composition of EPS proteins. Peak C has no obvious changes during granulation, while the fulvic-like substances present an increase in fluorescence intensities during storage, accompanied with an increase in structural complexity. The fulvie-like substances are also associated with the disintegration of the aerobic granules.

Chemical properties of colored dissolved organic matter in the sea-surface microlayer and subsurface water of Jiaozhou Bay, China in autumn and winter

The distribution and chemical properties of chromophoric dissolved organic matter （CDOM） in the Jiaozhou Bay, China were examined during four cruises in 2010-2011. The influence of freshwater and industrial and municipal sewage along the eastern coast of the bay was clearly evident as CDOM level- s （defined as a30s）, and dissolved organic carbon （DOC） concentrations were well correlated with salinity during all the cruises. Moreover, DOC concentrations were significantly correlated with chlorophyll a con- centrations in the surface microlayer as well as in the subsurface water. The concentrations of DOC and CDOM displayed a gradually decreasing trend from the northwestern and eastern coast to the central hay, and the values and gradients of their concentrations on the eastern coast were generally higher than those on the western coast. In addition, CDOM and DOC levels were generally higher in the surface microlayer than in the subsurface water. In comparison with DOC, CDOM exhibited a greater extent of enrichment in the microlayer in each cruise, with average enrichment factor （EF） values of 1.38 and 1.84, respectively. Four fluorescent components were identified from the surface microlayer and subsurface water samples and could be distinguished as peak A, peak T, peak B and peak M. For all the cruises, peak A levels were higher in the surface microlayer than in the subsurface water. This pattern of variation might be attributed to the terrestrial input.

Flocculating characteristic of activated sludge flocs:Interaction between Al^(3+) and extracellular polymeric substances

Aluminum flocculant can enhance the flocculating performance of activated sludge.However,the binding mechanism of aluminum ion（Al 3＋） and extracellular polymeric substances（EPS） in activated sludge is unclear due to the complexity of EPS.In this work,threedimensional excitation emission matrix fluorescence spectroscopy（3DEEM）,fluorescence quenching titration and Fourier transform infrared spectroscopy（FT-IR） were used to explore the binding behavior and mechanism between Al 3＋ and EPS.The results showed that two fluorescence peaks of tyrosineand tryptophan-like substances were identified in the loosely bound-extracellular polymeric substances（LB-EPS）,and three peaks of tyrosine-,tryptophanand humic-like substances were identified in the tightly boundextracellular polymeric substances（TB-EPS）.It was found that these fluorescence peaks could be quenched with Al 3＋ at the dosage of 3.0 mg/L,which demonstrated that strong interactions took place between the EPS and Al 3＋.The conditional stability constants for Al 3＋ and EPS were determined by the Stern-Volmer equation.As to the binding mechanism,the-OH,N-H,C=O,C-N groups and the sulfurand phosphorus-containing groups showed complexation action,although the groups in the LB-EPS and TB-EPS showed different behavior.The TB-EPS have stronger binding ability to Al 3＋ than the LB-EPS,and TB-EPS play an important role in the interaction with Al 3＋.

Assessing the dynamics of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn by EEMs-PARAFAC

In this study we have successfully characterized the fluorescent components of chromophoric dissolved organic matter(CDOM) in the Yellow Sea and the East China Sea in autumn using excitation-emission matrix fluorescence spectroscopy(EEMs) combined with parallel factor analysis(PARAFAC).PARAFAC aids the characterization of fluorescence CDOM by decomposing the fluorescence matrices into individual components.Four humic-like components(C1,C2,C3,and C4),one marine biological production component(C6),and two protein-like components(C5 and C7) were identified by PARAFAC.We researched the distributional patterns of fluorescence intensity,regression analyses between salinity,chlorophyll a concentration and fluorescence intensities of individual fluorophore,and regression analysis between salinity and fluorescence intensities percent of individual fluorophore.The results revealed that C2 and C4 showed conservative mixing behavior,while C1 and C3 possessed conservative mixing behavior in high salinity region and additional behavior in low and middle salinity region,which were considered to be derived from riverine and degradation of organic matter from resuspended and/or sinking particles and show non-conservative mixing behavior.In addition to riverine sources,the tryptophan-like C5 may receive widespread addition(likely from photo-degradation or biodegradation),while the most likely sources for the one marine humic-like C6 and tyrosine-like C7 were biological activity and microbial processing of plankton-derived CDOM,which were suggested to be of autochthonous origin and biologically labile.The application of EEM-PARAFAC modeling presents a unique opportunity to observe compositional changes,different mixing behavior and temporal variability in CDOM in the Yellow Sea and the East China Sea.

Evidence on the causes of the rising levels of COD_(Mn) along the middle route of the South-to-North Diversion Project in China:The role of algal dissolved organic matter

As the biggest inter-basin water transfer scheme in the world,the South-to-North Water Diversion Project(SNWD) was designed to alleviate the water crisis in North China.The main channel of the middle route of the SNWD is of great concern in terms of the drinking water quality.In this study,we tested the hypothesis that the dissolved organic matter(DOM) derived from the planktonic algae causes the rising levels of COD_(Mn) along the middle route by monitoring data on water quality(2015-2019,monthly resolution).The results showed that algal density in the main channel increased along the channel and was significantly correlated with COD_(Mn)(p <0.01).Five fluorescent components of DOM,including tyrosine-like(14.85%),tryptophan-like(22.48%),microbial byproduct-like(26.34%),fulvic acid-like(11.41%),and humic acid-like(24.92%) components,were detected.The level of tyrosine-like components increased along the channel and was significantly correlated with algal density(p<0.01),indicating that algae significantly changed the level of DOM in the channel.Algal decomposition and metabolism were found to be the main mechanisms that drive the changes in COD_(Mn).Therefore,controlling algal density would be an important measure to prevent further increase in CODMn and for the guarantee of excellent water quality.

Interactions between metal ions and the biopolymer in activated sludge： quantification and effects of system pH value

The quantification and effects of system pH value on the interactions between Pb（II） and the biopolymer in activated sludge were investigated. The biopolymer had two protein-like fluorescence peaks （Ex/Em = 280 nm1326-338 nm for peak A; Ex/Em = 220-230 nm/324-338 nm for peak B）. The fluorescence intensities of peak B were higher than those of peak A. The fluorophores of both peaks could be largely quenched by Pb（ll）, and the quencher dose for peak B was about half of that for peak A. The modified Stern-Volmer equation well depicted the fluorescence quenching titration. The quenching constant （Ka） values for both peaks decreased with rising system pH value, and then sharply decreased under alkaline conditions. It could be attributed to that the alkaline conditions caused the reduction of available Pb（II） due to the occurrence of Pb（OH）2 sediments. The Ka values of peak B were bigger than those for peak A at the same system pH values. Accordingly, the aromatic proteins （peak B） played a key role in the interactions between metal ions and the biopolymer.

Insights on the solubilization products after combined alkaline and ultrasonic pre-treatment of sewage sludge

This work provides insights on the solubilization products after a simultaneous combination of alkaline and ultrasonic （ALK ＋ ULS） pre-treatment of sewage sludge. Soluble chemical oxygen demand （SCOD） increased from 1200 to 11,000 mg/L after such treatment. Organics with molecular weight around 5.6 kDa were solubilized because of the synergistic effect of ultrasound and alkali. Organics with molecular weight larger than 300 kDa increased from 7.8% to 60%, 16% and 42.3% after ULS, ALK and ALK ＋ ULS treatment, respectively. Excitation emission matrix fluorescence spectroscopy analysis identified soluble microbial product-like and humic acid-like matters as the main solubilization products. Sludge anaerobic biodegradability was significantly enhanced with the simultaneous application of ALK ＋ ULS pre-treatment. ALK ＋ ULS pre-treatment resulted in 37.8% biodegradability increase compared to the untreated sludge. This value was higher compared to the biodegradability increase induced by individual ALK pre-treatment （5.7%） or individual ULS pre-treatment （20.7%） under the same conditions applied.

Spectroscopic study on transformations of dissolved organic matter in coal-to-liquids wastewater under integrated chemical oxidation and biological treatment process

A large amount of wastewater containing various toxic organic contaminants is produced during coal-to-liquids process. In this study, several spectroscopic methods were used to monitor the transformation of organic pollutants during an integrated chemical oxidation and biological process. The results showed that the hydrophobic acid fraction increased after Fenton oxidation, which was likely due to the production of small-molecule organic acids. Soluble microbial products were generated during biological treatment processes,which were degraded after ozonation; meanwhile, the hydrophilic base and acid components increased. Ultraviolet-visible spectroscopic analysis indicated that peaks at the absorption wavelengths of 280 and 254 nm, which are associated with aromatic substances, were detected in the raw water. The aromatic substances were gradually removed, becoming undetectable after biological aeration filter（BAF） treatment. Fourier transform infrared spectroscopy analysis revealed that the functional groups of phenols;benzene, toluene, ethylbenzene, and xylene（BTEX）; aromatic hydrocarbons; aliphatic acids;aldehydes; and esters were present in raw wastewater. The organic substances were oxidized into small molecules after Fenton treatment. Aromatic hydrocarbons were effectively removed through bioadsorption and biodegradation after BAF process.Biodegradable organic matter was reduced and finally became undetectable after anoxic–oxic treatment in combination with a membrane bioreactor. Four fluorescent components were fractionated and obtained via excitation–emission matrix parallel factor analysis（EEM-PARAFAC）. Dissolved organic matter fractionation in conjunction with EEM-PARAFAC was able to monitor more precisely the evolution of characteristic organic contaminants.

Extraction and characterization of bound extracellular polymeric substances from cultured pure cyanobacterium(Microcystis wesenbergii)

Preliminary characterization of bound extracellular polymeric substances（bEPS） of cyanobacteria is crucial to obtain a better understanding of the formation mechanism of cyanobacterial bloom. However,the characterization of bEPS can be affected by extraction methods. Five sets（including the control） of bEPS from Microcystis extracted by different methods were characterized using three-dimensional excitation and emission matrix（3DEEM） fluorescence spectroscopy combined chemical spectrophotometry; and the characterization results of bEPS samples were further compared. The agents used for extraction were NaOH,pure water and phosphate buffered saline（PBS） containing cationic exchange resins,and hot water. Extraction methods affected the fluorescence signals and intensities in the bEPS. Five fluorescence peaks were observed in the excitation and emission matrix fluorescence spectra of bEPS samples. Two peaks（peaks T1 and T2） present in all extractions were identified as protein-like fluorophores,two（peaks A and C） as humic-like fluorophores,and one（peak E） as a fulvic-like substance.Among these substances,the humic-like and fulvic-like fluorescences were only seen in the bEPS extracted with hot water. Also,NaOH solution extraction could result in strong fluorescence intensities compared to the other extraction methods. It was suggested that NaOH at pH 10.0 was the most appropriate method to extract bEPS from Microcystis. In addition,dialysis could affect the yields and characteristics of extracted bEPS during the determination process. These results will help us to explore the issues of cyanobacterial blooms.

Chemical identification and genotoxicity analysis of petrochemical industrial wastewater

The actual harmful effects of industrial waste- water can not be reflected by the conventional water quality index. Therefore, the change in dissolved organic matter and the genetic toxicity of petrochemical waste- water were observed in the current study by examining the wastewater treatment plant of a large petrochemical enterprise in Northwest China. Using XAD-8, MSC, and DA-7 resins, the wastewater was separated into six fractions, namely, hydrophobic acid （HOA）, hydrophobic neutral （HOB）, hydrophobic alkaline, hydrophilic acid, hydrophilic alkaline, and hydrophilic neutral. Umu-test was used to detect the genetic toxicity of the wastewater samples, and fluorescence spectra were also obtained to examine genetic toxic substances. The results show that wastewater treatment facilities can effectively reduce the concentration of organic matter in petrochemical waste- water （p 〈 0.05）. However, the mixing of aniline waste- water can increase the amount of organic carbon （p 〈 0.05） and can overload facilities. This finding shows that the mixed collection and joint treatment of different types of petrochemical wastewater can affect the water quality of the effluent. Particularly, hydrophobic substances can be difficult to remove and account for a relatively large proportion of the effluent. The mixture of aniline waste- water can increase the genetic toxicity of the effluent （p〈0.05）, and biologic treatment can not effectively decrease the toxicity. Most of the genetic toxicology may exist in the HOA and HOB fractions. Fluorescence spectroscopy also confirms this result, and tryptophan- like substances may play an important role in genetic toxicity.