Nanjing Zhao

Composition analysis of colored dissolved organic matter in Taihu Lake based on three dimension excitation-emission fluorescence matrix and PARAFAC model, and the potential application in water quality monitoring.

Taihu Lake is one of the five biggest lakes in China. Surface water samples from 26 sampling sites of Taihu Lake were collected. Furthermore wet chemical analysis (COD(Cr) and BOD5) and measurement of three dimensional excitation-emission matrix (3DEEM) spectra in the laboratory have been conducted. Using parallel factor analysis (PARAFAC) model, three components of colored dissolved organic matter (CDOM) have been identified successfully, based on the analysis of 3DEEM data. The characteristics of the three components also have been described by comparing them to some components of CDOM, identified in earlier researches. Meanwhile, spatial variations of concentration for the three components in Taihu Lake have been analyzed, and the result indicates that the concentration of component 1 depends more on the situation of wastewater pollution and can be used as the indicator of wastewater pollution. The relationship between the concentrations of the three components and results of the wet chemical analysis show that none of the three components can be used as indicators of gross organic matter in water. However, the concentrations of all the three components have obvious linear relationships with the BOD5 value, especially for component 1 (r = 0.72878). Finally, the potential applications of the composition analysis based on 3DEEM and PARAFAC model in water quality monitoring have been illuminated.

Hydrothermal synthetic mercaptopropionic acid stabled CdTe quantum dots as fluorescent probes for detection of Ag

Mercaptopropionic acid (MPA) capped CdTe quantum dots (QDs) with particle size 3 nm have been successfully synthesized in aqueous medium by hydrothermal synthesis method. And the effects of different metal ions on MPA capped CdTe QDs fluorescence were studied using fluorescence spectrometry. The results demonstrated that at the same concentration level, Ag(+) could strongly quench CdTe QDs fluorescence, and the other metal ions had little effect on CdTe QDs fluorescence except Cu(2+). On the basis of this fact, a rapid, simple, highly sensitive and selective method based on fluorescence quenching principle for Ag(+) detection in aqueous solution was proposed. Under optimal conditions, the quenched fluorescence intensity (F(0)-F) increased linearly with the concentration of Ag(+) ranging from 4 × 10(-7) to 32 × 10(-7)mol L(-1). The limit of detection for Ag(+) was 4.106 × 10(-8)mol L(-1). The obtained plot of F(0)/F versus [Ag(+)] was an upward curvature, concave towards the y-axis, rather than a straight line. The modified form of the Stern-Volmer equation was third order in Ag(+) concentration. According to the modified Stern-Volmer equation, it can be inferred that dynamic quenching and static quenching simultaneously occurred when Ag(+) interacted with MPA capped CdTe QDs. At the same time other factors might also influence the quenching process. Based on this study, hydrothermal synthesized MPA capped CdTe QDs with particle size 3 nm may be used as a novel fluorescence probe to quantificationally and selectively detect Ag(+).

In Situ Underwater Laser-Induced Breakdown Spectroscopy Analysis for Trace Cr(VI) in Aqueous Solution Supported by Electrosorption Enrichment and a Gas-Assisted Localized Liquid Discharge Apparatus

Traditional laser-induced breakdown spectroscopy (LIBS) always fails to directly detect target in aqueous solution due to rapid quenching of emitted light and adsorption of pulse energy by surrounding water. A method is proposed for the in situ underwater LIBS analysis of Cr(VI) in aqueous solution freed from the common problems mentioned above by combining a gas-assisted localized liquid discharge apparatus with electrosorption for the first time. In this approach, the introduction of the gas-assisted localized liquid discharge apparatus provides an instantaneous gaseous environment for underwater LIBS measurement (that is, the transfer of sampling matrix is not needed from aqueous solution to dry state). The preconcentration of Cr(VI) is achieved by electrosorption with a positive potential applied around adsorbents, which can promote the adsorption of Cr(VI) and inhibit that of the coexisting cations leading to a good anti-interference. Amino groups functionalized chitosan-modified graphene oxide (CS-GO) is utilized for Cr(VI) enrichment, which can be protonated to form NH3+ in acidic condition promoting the adsorption toward Cr(VI) by electrostatic attraction. The highest detection sensitivity of 5.15 counts μg-1 L toward Cr(VI) is found for the optimized electrosorption potential (EES = 1.5 V) and electrosorption time (tES = 600 s) without interference from coexisting metal ions. A corresponding limit of detection (LOD) of 12.3 μg L-1 (3σ method) is achieved, which is amazingly improved by 2 or even 3 orders of magnitude compared to the previous reports of LIBS.

A novel initialization method for nonnegative matrix factorization and its application in component recognition with three-dimensional fluorescence spectra

Nonnegative matrix factorization has been widely used in many areas and has been applied for component recognition with three dimensional fluorescence spectra recently. However, nonnegative matrix factorization is a nonconvex programming in the iteration process, thus the solution is dependent on the initial values and consequently not unique. Up to now, an effective global convergent algorithm is still absent. In this work, we propose an initialization scheme based on independent component analysis. Compared with other initialization schemes, the optimal solution of nonnegative matrix factorization based on independent component analysis is much better and it is demonstrated by typical experiments of component recognition with three-dimensional fluorescence spectra.

Determination of polycyclic aromatic hydrocarbons by four-way parallel factor analysis in presence of humic acid

There is not effective method to solve the quenching effect of quencher in fluorescence spectra measurement and recognition of polycyclic aromatic hydrocarbons in aquatic environment. In this work, a four-way dataset combined with four-way parallel factor analysis is used to identify and quantify polycyclic aromatic hydrocarbons in the presence of humic acid, a fluorescent quencher and an ubiquitous substance in aquatic system, through modeling the quenching effect of humic acid by decomposing the four-way dataset into four loading matrices corresponding to relative concentration, excitation spectra, emission spectra and fluorescence quantum yield, respectively. It is found that Phenanthrene, pyrene, anthracene and fluorene can be recognized simultaneously with the similarities all above 0.980 between resolved spectra and reference spectra. Moreover, the concentrations of them ranging from 0 to 8μgL(-1) in the test samples prepared with river water could also be predicted successfully with recovery rate of each polycyclic aromatic hydrocarbon between 100% and 120%, which were higher than those of three-way PARAFAC. These results demonstrate that the combination of four-way dataset with four-way parallel factor analysis could be a promising method to recognize the fluorescence spectra of polycyclic aromatic hydrocarbons in the presence of fluorescent quencher from both qualitative and quantitative perspective.

Component recognition with three-dimensional fluorescence spectra based on non-negative matrix factorization

Non‐negative matrix factorization (NMF) is a widely used approach in signal processing. In this work, we apply it to the component recognition of mixtures with multicomponent three‐dimensional fluorescence spectra. Compared with the popular PARAFAC for component recognition, NMF has the following advantages: on one hand, the decomposed spectra are three dimensional, and thus, more information can be obtained, which is beneficial for component recognition; on the other hand, the decomposed spectra are non‐negative and thus have a certain physical significance. More importantly, we propose a type of integrated similarity indices for the three‐dimensional fluorescence spectra, which, by construction, is good at component recognition from overlapping fluorescence spectra. Experiment results demonstrate that NMF combined with integrated similarity index provides an effective method for component recognition of multicomponent three‐dimensional overlapping fluorescence spectra. Copyright

Mercaptopropionic acid-capped Mn-doped ZnS quantum dots as a probe for selective room-temperature phosphorescence detection of Pb2+ in water

In this study, highly water-soluble Mn-doped ZnS quantum dots (QDs) capped by 3-mercaptopropionic acid (MPA) were successfully synthesized by three different synthetic methods. By comparison, QDs prepared by hydrothermal synthesis method at 100 °C heating for 2 h had the best phosphorescence emission properties. Room-temperature phosphorescence (RTP) could be remarkably and selectively quenched by Pb2+ in a pH 3.8 NaAc–HAc buffer solution. Based on the abovementioned finding, a simple, sensitive, and selective phosphorescence method for rapid detection of Pb2+ was successfully developed using MPA-capped Mn-doped ZnS QDs as a probe. Under the optimized conditions, the RTP intensity ratio of P0/P had a good linear relationship with Pb2+ concentration in the concentration ranges of 4 × 10−8–90 × 10−8 mol L−1 and 90 × 10−8–600 × 10−8 mol L−1 with the correlation coefficients of 0.9967 and 0.9970, which well followed the Stern–Volmer quenching equation, and the Stern–Volmer quenching constants were 8.41 × 105 L mol−1 and 3.452 × 106 L mol−1, respectively. The detection limit was 3.69 × 10−8 mol L−1, and the relative standard deviation for 11 repeated detections of 60 × 10−8 mol L−1 Pb2+ was 2.8%. According to the analysis of the Stern–Volmer quenching equation, UV-Vis absorption spectra, decay curves of phosphorescence emission, and phosphorescence lifetime, the quenching mechanism may imply that energy transfer and charge transfer in the interaction of MPA-capped Mn-doped ZnS QDs at the excited state with Pb2+ made QDs lose excitation energy. This resulted in phosphorescence of QDs causing dynamic quenching. The proposed method was successfully applied to detect Pb2+ in real water samples with satisfactory results, and the recoveries ranged from 93% to 109.3%. The developed method was simple, rapid, and specific and could effectively avoid fluorescence interference of the system, which opened up a promising prospect for the sensitive, convenient, and fast sensing and monitoring of small molecule pollutants in water based on phosphorescence sensors.

Quantifying PAHs in water by three-way fluorescence spectra and second-order calibration methods

It is still difficult to determine the concentrations of polycyclic aromatic hydrocarbons accurately in natural water by fluorescence technique because of their low solubility, different fluorescent intensity, and the complex interferents from water environments. In this work, three-way fluorescence spectra combined with three methods including three-way parallel factor analysis, multi-way partial least square with residual bilinearization and unfolded partial least square with residual bilinearization were used to predict the concentrations of polycyclic aromatic hydrocarbons at the μg L-1 level in reservoir and river water, respectively. The prediction abilities of these methods on different analytes were evaluated by validation sets. The results demonstrate that unfolded partial least square with residual bilinearization yields the optimal results with relative error less than or equal to 6% for phenanthrene, pyrene, anthracene and fluorene, and 35% for acenaphthene and fluoranthene in different water backgrounds.

Measurements of aerosol distribution by an elastic-backscatter lidar in summer 2008 in Beijing

Elastic lidar observations of profiles of the aerosol extinction, backscattering coefficients, and the lidar ratio have been performed in Beijing. The elastic lidar transmitts wavelengths of 532 and 355 nm. The measurement altitude can reach up to 6 km. The similarity of the extinction and backscattering profiles suggests a close relation between the mean transmission and reflection properties. The lidar ratio on July 22, 2008 varied from 10 to 30 sr with the mean value of 20 sr. The profiles of the aerosol properties indicate the cirrus at 6-km altitude and a well-mixed boundary layer from July 22 to 24, 2008. The detected boundary layer also agrees well with the high and stable ozone concentration obtained from the differential optical absorption spectroscopy (DOAS) system.

Monitoring the Heavy Element of Cr in Agricultural Soils Using a Mobile Laser-Induced Breakdown Spectroscopy System with Support Vector Machine

Due to its complicated matrix effects, rapid quantitative analysis of chromium in agricultural soils is difficult without the concentration gradient samples by laser-induced breakdown spectroscopy. To improve the analysis speed and accuracy, two calibration models are built with the support vector machine method: one considering the whole spectra and the other based on the segmental spectra input. Considering the results of the multiple linear regression analysis, three segmental spectra are chosen as the input variables of the support vector regression (SVR) model. Compared with the results of the SVR model with the whole spectra input, the relative standard error of prediction is reduced from 3.18% to 2.61% and the running time is saved due to the decrease in the number of input variables, showing the robustness in rapid soil analysis without the concentration gradient samples.