The Evaluation for Alterations of DOM Components from Upstream to Downstream Flow of Rivers in Toyama (Japan) Using Three-Dimensional Excitation-Emission Matrix Fluorescence Spectroscopy

The dissolved organic matter (DOM) is one of the important factors for controlling water quality. The behavior and constitutions of DOM is related to the risk of human health because it is able to directly or indirectly affect the behavior, speciation and toxicity of various environmental pollutants. However, it is not easy to know the contents of DOM components without using various complicated and time consuming analytical methods because DOM is a complex mixture and usually exists at low concentration. Here, we describe the fluorescence properties of DOM components in water samples collected from four rivers in Toyama, Japan by means of the three-dimensional excitation-emission matrix (3DEEM) fluorescence spectroscopy. In order to evaluate the alterations of DOM components in each of the river during the flow from upstream to downstream, the patterns of relative fluorescence intensity (RFI) at six peaks which are originated from fluorophores including humic-like and protein-like components were investigated. The changes in the patterns of RFI values at each of the peak and the concentration of dissolved organic carbon (DOC) for each river water sample were discussed in connection with the differences of land use managements and basic water quality parameters, such as pH, EC, turbidity, Fe3+, T-N, NO3-N, T-P, PO4-P, chlorophyll a, DOC and N/P ratio. The DOC concentrations in the water samples collected from these rivers were relatively low (0.63–1.16 mg/L). Two main peaks which have a strong RFI value expressed a positive correlation with the DOC concentration (r = 0.557, 0.535). However, the correlations between the RFI values for other four peaks and the DOC concentration were below 0.287. The alterations of DOM components during the flow of a river from upstream to downstream were investigated from the changes in the patterns of RFI values for six fluorescent peaks. It was clarified that the great increase of RFI values in peak A and peak T from river water located in urban area showed high concentration of PO4-P and Fe3+, and low N/P ratio due to the high biological activities. The values of fluorescence index (FIX) and biological index (BIX) were as high as 1.60 and 0.72, respectively

Influence of temperature and applied potential on the permeability of polyphenol films prepared on vitreous carbon in acid and alkaline media

The electrochemical polymerization of phenol is known to rapidly produce a thin insulating film at the anode surface. This film generally blocks further polymerization. The objective of this study is to show that, depending on the operating conditions, polymeric films resulting from phenol oxidation present different properties and that certain films can be so porous that they allow the oxidation of phenol to continue. The deposition of polyphenol films with improved permeability could be attractive in the removal of phenol from polluted solutions. Polyphenol films were prepared in aqueous solution on a vitreous carbon anode either by cyclic voltammetry or by electro-oxidation at constant potential. The apparent permeability P (%) of the films prepared by these techniques was evaluated by monitoring changes in the electrode response towards phenol and potassium ferricyanide at 25 and 85°C and as a function of the potential applied during electropolymerization performed either in acidic (1 mol L-¹H₂SO₄) or in alkaline (1 mol L-¹ NaOH) aqueous solution. It was shown that: (1) the polyphenol film electrosynthesized in alkaline medium was more permeable than that prepared in acidic medium, (2) the apparent permeability was higher when the polyphenol film was electrosynthesized with simultaneous oxygen evolution and (3) the use of a high temperature in the polyphenol film preparation, especially in the presence of a concomitant oxygen evolution, significantly enhanced its apparent permeability (P ≥ 100 %). These results are interpreted in terms of a mixed-transport mechanism involving both pore and membrane diffusion. The effect of the permeability of the polymeric film on the removal of phenol from aqueous solution by electropolymerization is discussed

Influence of temperature and applied potential on the permeability of polyphenol films prepared on vitreous carbon in acid and alkaline media

The electrochemical polymerization of phenol is known to rapidly produce a thin insulating film at the anode surface. This film generally blocks further polymerization. The objective of this study is to show that, depending on the operating conditions, polymeric films resulting from phenol oxidation present different properties and that certain films can be so porous that they allow the oxidation of phenol to continue. The deposition of polyphenol films with improved permeability could be attractive in the removal of phenol from polluted solutions. Polyphenol films were prepared in aqueous solution on a vitreous carbon anode either by cyclic voltammetry or by electro-oxidation at constant potential. The apparent permeability P (%) of the films prepared by these techniques was evaluated by monitoring changes in the electrode response towards phenol and potassium ferricyanide at 25 and 85°C and as a function of the potential applied during electropolymerization performed either in acidic (1 mol L-¹H₂SO₄) or in alkaline (1 mol L-¹ NaOH) aqueous solution. It was shown that: (1) the polyphenol film electrosynthesized in alkaline medium was more permeable than that prepared in acidic medium, (2) the apparent permeability was higher when the polyphenol film was electrosynthesized with simultaneous oxygen evolution and (3) the use of a high temperature in the polyphenol film preparation, especially in the presence of a concomitant oxygen evolution, significantly enhanced its apparent permeability (P ≥ 100 %). These results are interpreted in terms of a mixed-transport mechanism involving both pore and membrane diffusion. The effect of the permeability of the polymeric film on the removal of phenol from aqueous solution by electropolymerization is discussed

New fluorometric enzyme immunoassay for 17β-estradiol by homogeneous reaction using biotinylated estradiol

A new fluorometric enzyme immunoassay for 17β-estradiol (E2) using biotinylated estradiol (BE) as a probe ligand, is described. In this method, E2 is detected indirectly by a solid-phase avidin-biotin binding assay, in which the biotin is immobilized on a microtiter plate (biotin-plate). After the competitive reaction between E2 and BE for the anti-E2 antibody in solution, the free E2 and BE are separated from the bound forms by means of ultrafiltration. The concentration of BE in the solution is determined from the reaction between the biotin immobilized on the plate and the free BE for the limited biotin binding sites of avidin conjugated with horseradish peroxidase (avidin-HRP), which is added to the solution. The enzymatic reaction of HRP was TM measured by a fluorometric analysis with the QuantaBlu Fluorogenic Peroxidase Substrate (QFPS) in order to detect of the avidin-biotin binding with a high degree of sensitivity. The detection limit and linear range for the determination of E2 were 0.12 nM and from 0.12 to 25 nM, respectively. The relative standard deviations (RSD) for the E2 assay were between 2.2 and 9.1% (n = 3). The cross-reactivity for several other estrogens was also evaluated

Hydrodynamic Voltammetry as a Rapid and Simple Method for Evaluating Soil Enzyme Activities

Soil enzymes play essential roles in catalyzing reactions necessary for nutrient cycling in the biosphere. They are also sensitive indicators of ecosystem stress, therefore their evaluation is very important in assessing soil health and quality. The standard soil enzyme assay method based on spectroscopic detection is a complicated operation that requires the removal of soil particles. The purpose of this study was to develop a new soil enzyme assay based on hydrodynamic electrochemical detection using a rotating disk electrode in a microliter droplet. The activities of enzymes were determined by measuring the electrochemical oxidation of p-aminophenol (PAP), following the enzymatic conversion of substrate-conjugated PAP. The calibration curves of β-galactosidase (β-gal), β-glucosidase (β-glu) and acid phosphatase (AcP) showed good linear correlation after being spiked in soils using chronoamperometry. We also performed electrochemical detection using real soils. Hydrodynamic chronoamperometry can be used to assess the AcP in soils, with a detection time of only 90 s. Linear sweep voltammetry was used to measure the amount of PAP released from β-gal and β-glu by enzymatic reaction after 60 min. For the assessment of soil enzymes, the results of hydrodynamic voltammetry assay compared favorably to those using a standard assay procedure, but this new procedure is more user-friendly, rapid and simple