Development of absorption spectrophotometry of iron(III) in environmental water and sediments using NEDA and its application to the field.

In this study, we developed a simple method that enables iron(III) in environmental water to be directly determined via spectrophotometry. In water samples, iron(III) formed a yellowish complex with N-1-Naphthylethylenediamine dihydrochloride (NEDA) at pH 2.0-2.8, the maximum absorption wavelength of which was 462 nm. Detection sensitivity increased in the presence of chloride ions and remained constant for 2-24 h with 0.05-0.57 mol L-1 chloride. Therefore, NEDA solution containing chloride ions was used as a chromogenic reagent for the determination of iron(III). The determination range for this method was 0.1-20 mgFe(III) L-1 in a 5 cm glass cell. The developed method is highly selective for iron(III) and has been successfully applied to freshwater, brackish water, seawater, turbid water in rivers, as well as to riverbed and freshwater lake sediments. In addition, a combination of the proposed NEDA method and the 1,10-phenanthroline method enabled simultaneous determination of iron(III) and iron(II).

Phylogenetic Analysis and Characterization of Odorous Compound-Producing Actinomycetes in Sediments in the Sanbe Reservoir, A Drinking Water Reservoir in Japan.

Odor caused by the presence of geosmin and 2-methylisoborneol (2-MIB) in aquatic ecosystems leads to considerable economic loss worldwide. The odorous compounds are primarily produced by cyanobacteria and actinomycetes. While the contribution of odorous compounds-producing cyanobacteria has been thoroughly investigated, the production of geosmin and 2-MIB by actinomycetes in aquatic ecosystems is poorly understood. In this study, we isolated geosmin and/or 2-MIB-producing actinomycetes in sediments collected from the Sanbe Reservoir, Japan, identified the biosynthetic gene of geosmin and 2-MIB, and investigated the production of the odorous compounds by the isolated strains. Partial sequence of 16S rRNA and the biosynthetic genes was determined to analyze the phylogenetic relationship among the strains. The geosmin and 2-MIB concentrations in the culture of the isolated strains were measured using gas chromatography mass spectrometry. Fifty-four strains of odorous compounds-producing and non-geosmin-producing actinomycetes were isolated from sediments from the Sanbe Reservoir. Diverse actinomycetes were identified and many of them produced geosmin and/or 2-MIB. Many odorous compounds-producing actinomycetes were phylogenetically different from previously reported producing actinomycetes. The producing ability of the odorous compounds of the isolated strains in this study was not significantly related with the phylogenetic groups of 16S rRNA and the biosynthetic genes. The findings suggest that the odorous compounds-producing actinomycetes in the sediments are diverse and different from previously reported strains.

Sensitive Gas Chromatography Detection of Nanomolar Hydroxylamine in Environmental Water by Fe(III) Oxidation.

Nanomolar concentrations of NH2OH in natural water sources were determined using an Fe3+ oxidation method. A pH of 2.35 - 2.50 was used, which was adjusted by adding a chloroacetate buffer. Equal amounts (1.0 mL) of the chloroacetate solution and ferric chloride solution were added to the water sample (70 mL) to oxidize NH2OH to N2O. The resulting N2O in the sample water was then quantified by headspace analysis using a gas chromatograph with an electron-capture detector (ECD), where a limit of detection of 0.2 µgN L-1 (14 nmol L-1) was achieved. This method was successfully applied to samples of freshwater, brackish water, and seawater, and despite the various salinities no interfering substances were observed. Furthermore, NH2OH was successfully detected in samples collected from the Hii River and Lakes Shinji and Nakaumi (Shimane Prefecture, Japan). In addition, the proposed method was also applicable to samples rich in organic substance derived from phytoplankton.

Sensitive Method for the Oxidation-determination of Trace Hydroxylamine in Environmental Water Using Hypochlorite Followed by Gas Chromatography.

We developed a method for quantifying trace NH2OH in brackish- and sea-water samples. Previously reported methods applicable to fresh water cannot be applied to such samples. We determined that interference in seawater owing to the bromide ion can be removed by the addition of phenol. In our procedure, phenol and hypochlorite solutions were added to a sample solution to oxidize NH2OH to N2O. N2O in the sample was then quantified by headspace analysis. The method is not affected by the salt content or ammonia, nitrate, or nitrite at concentrations of 300 µgN L-1 or less. It has a limit of detection of 0.2 µgN L-1, and can quantify NH2OH in natural water samples with a wide range of salinity. It was applied to samples from Lake Nakaumi, a brackish lake located in the eastern part of Shimane Prefecture, Japan.

Determination of Trace Hydrazine in Environmental Water Samples by in situ Solid Phase Extraction.

A simple and rapid in situ method for the determination of hydrazine based on the concentration of aldazine compound formed by the reaction of hydrazine with p-dimethylaminobenzaldehyde was developed. This method was based on solid-phase extraction using a Sep-Pak C18 cartridge, followed by the quantification of hydrazine using a spectrophotometric method. To a sample solution of environmental water, p-dimethylaminobenzaldehyde solution was added to form aldazine by the reaction with hydrazine. The solution was passed through a Sep-Pak C18 cartridge for the adsorption of aldazine. In the laboratory, the aldazine adsorbed on the Sep-Pak C18 cartridge was eluted by passing a hydrochloric acid-ethanol (1:10) solution through the cartridge, and the color intensity of the solution was measured at 457 nm. The limit of detection for the new method was 0.2 mgN L-1 of hydrazine. The determination of hydrazine in solution was not influenced even by hydrogen sulfide and organic matter. This method was then applied to the brackish water of Lake Nakaumi in the eastern area of Shimane Prefecture, Japan. This method was used to determine hydrazine in freshwater, seawater and wastwater.

High spatial resolution analysis of the distribution of sulfate reduction and sulfide oxidation in hypoxic sediment in a eutrophic estuary.

Bottom hypoxia and consequential hydrogen sulfide (H2S) release from sediment in eutrophic estuaries is a major global environmental issue. We investigated dissolved oxygen, pH and H2S concentration profiles with microsensors and by sectioning sediment cores followed by colorimetric analysis. The results of these analyses were then compared with the physicochemical properties of the bottom water and sediment samples to determine their relationships with H2S production in sediment. High organic matter and fine particle composition of the sediment reduced the oxidation-reduction potential, stimulating H2S production. Use of a microsensor enabled measurement of H2S concentration profiles with submillimetre resolution, whereas the conventional sediment-sectioning method gave H2S measurements with a spatial resolution of 10 mm. Furthermore, microsensor measurements revealed H2S consumption occurring at the sediment surface in both the microbial mat and the sediment anoxic layer, which were not observed with sectioning. This H2S consumption prevented H2S release into the overlying water. However, the microsensor measurements had the potential to underestimate H2S concentrations. We propose that a combination of several techniques to measure microbial activity and determine its relationships with physicochemical properties of the sediment is essential to understanding the sulfur cycle under hypoxic conditions in eutrophic sediments.

Colorimetric Determination of Sulfide in Microsamples.

A method for determination of hydrogen sulfide in microsamples (200 µL) was developed by modifying the methylene blue method. Samples were collected using a micropipette and were combined with sulfide coloring reagent and 5 mL of 0.1 M HCl in test tubes. Absorbance of the solution was measured spectrophotometrically at 667 nm. This modified method did not require any special labware or technique, and can be used in a variety of research fields.

Adsorptive removal of cadmium by natural red earth: equilibrium and kinetic studies.

Natural red earth (NRE), an iron-coated sand found in the north western part of Sri Lanka, was used to examine the retention behaviour of cadmium, a heavy metal postulated as a factor of chronic kidney disease in Sri Lanka. Adsorption studies were conducted as a function of pH, ionic strength, initial Cd loading and time. The Cd adsorption increased from 6% to 99% with the pH increase from 4 to 8.5. The maximum adsorption was reached at pH > 7.5. Cadmium adsorption was not changed over 100-fold variations of NaNO3, providing evidence for the dominance of an inner-sphere bonding mechanism for both 10-fold variation of initial Cd concentrations. Surface complexation modelling suggests a monodentate bonding mechanism. Isotherm data were fairly fitted to a two-site Langmuir isotherm model and sorption maximums of 9.11 x 10(-6) and 3.89 x 10(-7) mol g(-1) were obtained for two surface sites. The kinetic study reveals that Cd uptake by NRE is so fast that the equilibrium was reached within 15 min and - 1 h for 4.44 and 44.4 microM initial Cd concentrations, respectively, and the chemisorption was the dominant mechanism over intra-particle diffusion. The study indicates the potential of NRE as a material for decontaminating environmental water polluted with Cd.

Fluxes of carbon dioxide, methane and nitrous oxide in two contrastive fringing zones of coastal lagoon, Lake Nakaumi, Japan.

We measured fluxes of carbon dioxide (CO(2)), methane (CH(4)), and nitrous oxide (N(2)O) simultaneously in two typical fringing zones, sandy shore and salt marsh, of coastal lagoon, Lake Nakaumi, Japan, in mid-summer 2003. Our aim was to quantify net the greenhouse gases (GHGs) fluxes and examine key factors, which control variation of the GHGs fluxes in the two sites. Net CO(2) and CH(4) fluxes were markedly different between the two sites; magnitudes and variations of the both fluxes in sandy shore were lower than those of salt marsh. Meanwhile, magnitude and variation of net N(2)O flux in the two sites were similar. In sandy shore, temporal and spatial variation of the three GHGs fluxes were highly controlled by water level fluctuation derived from astronomic tide. In salt marsh, spatial variation of the three GHGs fluxes were correlated with aboveground biomass, and temporal variation of CO(2) and CH(4) fluxes were correlated with soil temperature. The sum of global warming potential, which was roughly estimated using the observed GHGs fluxes, was ca. 174-fold higher in salt marsh than in sandy shore.

Concentrations of arsenic in brackish lake water: application of tristimulus colorimetric determination.

The evaluation of a simple and rapid tristimulus colorimetric method for the determination of arsenic in brackish waters and its application to brackish water samples taken from brackish Lake Nakaumi are described. The determinations of arsenic in brackish water samples were made satisfactorily independent of sample salinity. By applying this method to lake water samples, the distributions and behaviors of arsenic in the lake and their controlling factors were clarified, such as seasonal variations of arsenic and the effect of a typhoon.

A simple and rapid in situ preconcentration method for trace ammonia nitrogen in environmental water samples using a solid-phase extraction followed by spectrophotometric determination.

A simple and rapid in situ preconcentration method for the spectrophotometric determination of trace ammonia nitrogen in environmental water samples has been developed based on solid-phase extraction using a small column packed with octadecyl group-bonded silica gel (Sep-Pak C18 cartridge). A water sample was taken into a graduated syringe for easy and simple operation and prevention of contamination immediately after sample collection. Ammonia in the sample was reacted with hypochlorite and thymol to be converted into indothymol blue; then the formed indothymol blue was collected as an ion pair between indothymol blue and tetrabutylammonium ion on a Sep-Pak C18 cartridge. The indothymol blue on the cartridge was stable for 4 days. The retained indothymol blue was easily eluted with a mixture of methanol and 0.01 mol/l sodium hydroxide solution. The color intensity due to the indothymol blue was spectrophotometrically measured at 725 nm. The proposed method was successfully applied to environmental water samples such as river water.

The liquid-liquid extraction using hydrophilic solvents occluded to an oil-adsorbent as an organic phase: extraction of 8-quinolinolato complexes of alkaline earth metals into tetrahydrofuran.

In order to use a hydrophilic solvent as an organic phase in liquid-liquid extraction by retaining it to a solid support, the occlusion and desorption of nine hydrophilic solvents, such as methanol, to three kinds of commercially available oil-adsorbent were examined. The combination of tetrahydrofuran and WOSEP made by fibrous polypropylene was finally selected, and was subjected to the extraction of alkaline Earth metals with 8-quinolinol. It was proved that Mg2+, Ca2+, and Sr2+ ions could be successfully extracted into the tetrahydrofuran phase in the form of 8-quinolinolato complexes, which could not be extracted into CHCl3.

Fibroblast growth factor receptor 3 protein expression in urothelial carcinoma of the urinary bladder, exhibiting no association with low-grade and/or non-invasive lesions.

Activating mutations of fibroblast growth factor receptor 3 (FGFR3), found in autosomal dominant human skeletal dysplasia, were reported to be involved in tumorigenesis and correlate with low-grade and superficial lesions of urothelial carcinoma. FGFR3 protein expression was immunohistochemically investigated in 126 cases of urothelial carcinoma of the urinary bladder to evaluate the role of this receptor in tumor behavior. p53 expression and the proliferating activity of tumor cells, assessed by Ki-67 expression, were also analyzed in parallel. Cytoplasmic and/or membrane immunostaining for FGFR3 was observed in 62 (49.2%) cases, including 20 (15.9%) cases of intense staining and 42 (33.3%) of moderate staining. p53 expression and Ki-67 labeling index (LI) were significantly correlated with high tumor grade (p=0.0093 and <0.0001, respectively) and invasion (p=0.0041 and <0.0001, respectively). Although there were two groups of interesting cases: low-grade and non-invasive tumors negative for p53 but positive for FGFR3, and high-grade and invasive tumors positive for p53 but negative for FGFR3, no statistically significant relationship was found between FGFR3 expression and tumor grade, invasion, p53 expression or Ki-67 LI. These results suggest that FGFR3 protein expression in bladder cancer is unlikely to affect tumor behavior as a unique single factor.

A simple and sensitive method for the determination of hydroxylamine in fresh-water samples using hypochlorite followed by gas chromatography.

A new and simple method for the determination of hydroxylamine in environmental water, such as fresh rivers and lakes using hypochlorite, followed by its gas choromatographic detection, has been developed. A glass vial filled with sample water was sealed by a butyl-rubber stopper and aluminum cap without head-space, and then sodium hypochlorite solution was injected into the vial through a syringe to convert hydroxylamine to nitrous oxide. The head-space in the glass vial was prepared with 99.9% grade N2 using a gas-tight syringe. After the glass vial was shaken for a few minutes, nitrous oxide in the gas-phase was measured by a gas chromatograph with an electron-capture detector. The dissolved nitrous oxide in the liquid-phase was calculated according to the solubility formula. The proposed method was applied to the analysis of fresh-water samples taken from Iu river and Hii river, flowing into brackish Lakes Nakaumi and Shinji, respectively.

A simple in situ visual and tristimulus colorimetric method for the determination of trace arsenic in environmental water after its collection on a mercury(II)-impregnated paper.

A simple in situ visual and tristimulus colorimetric method for the determination of trace arsenic in environmental water after collecting arsenic on a test paper impregnated with mercury(II) bromide and rosaniline chloride by its reduction aeration has been developed. The color development on the test paper is based on the formations of AsH(HgBr)2 (yellow) and/or As(HgBr)3 (brownish yellow) by a reaction between mercury(II) bromide and arsine (AsH3), which is produced through the reduction of As(III) (arsenite ion) and/or As(V) (arsenate ion) in a sample solution. To a sample solution, potassium iodide, tin(II) chloride, zinc sand and 4 ml of 6 M hydrochloric acid solution were added successively. The liberated arsine was collected on the test paper. The yellow or brownish-yellow color intensity on the test paper was measured by a tristimulus colorimeter and also by a visual method. The established method is applicable to the determination of arsenic in environmental water sample such as river, brackish, and seawater types.

A simple and rapid in situ preconcentration method using solid-phase extraction for the determination of dissolved manganese in brackish lake water samples.

A simple and rapid in situ preconcentration method for the determination of dissolved manganese in environmental waters has been developed based on solid-phase extraction using a Sep-Pak C18 cartridge. Manganese in water samples, which was taken into a graduated syringe to easily perform the operation for collecting manganese at sampling sites, was converted into a stable complex with 4-(2-pyridylazo)resorcinol (PAR) at pH 10 immediately after sample collection. The formed Mn-PAR complex was collected by a Sep-Pak C18 cartridge, which was packed with C18-bonded silica. The complex was stable in the Sep-Pak C18 cartridge for at least one month. The retained complex was quantitatively eluted with 0.5 M hydrochloric acid. The manganese was determined by graphite-furnace AAS. The proposed method was successfully applicable to brackish lake water samples to investigate the behavior of dissolved manganese in brackish lakes.