Capillary zone electrophoresis determination of fluoride in seawater using transient isotachophoresis.

We developed capillary zone electrophoresis (CZE) with indirect UV detection for the determination of fluoride (F-) in seawater using transient isotachophoresis (tITP) as an on-line concentration procedure. A method of correcting sample salinity effects was also proposed so that F- concentrations were obtained using a calibration graph. The proposed method is simple: it requires no sample pretreatment aside from dilution. The following optimum conditions were established: background electrolyte (BGE), 5 mM 2,6-pyridinedicarboxylic acid (PDC) adjusted to pH 3.5 containing 0.03% m/v hydroxypropyl methylcellulose (HPMC); detection wavelength, 200 nm; vacuum (50 kPa) injection period of sample, 5 s (254 nL); and applied voltage, 23 kV with the sample inlet side as the cathode. The limit of detection (LOD, S/N = 3) and limit of quantification (LOQ, S/N = 10) for F- reached 0.024 and 0.070 mg/L, respectively. The respective values of the relative standard deviation (RSD) of the peak area, peak height, and migration time for F- were 2.5, 3.4, and 0.30%. The proposed method was applied for the determination of F- in seawater samples collected from coastal waters of western Japan during August 26-28, 2014. Both results obtained using standard addition method and a calibration graph agreed with those obtained using a conventional spectrophotometric method.

Analysis of change of red tide species in Yodo River estuary by the numerical ecosystem model.

Occurrence number of red tides in Osaka Bay in Japan is more than 20 cases every year. Diatom red tide was dominant in Osaka Bay, but the non-diatom red tide was dominant in early 1990s. Therefore, the material cycling in Yodo River estuary in Osaka Bay during August from 1991 to 2000 was analyzed by using the numerical ecosystem model and field observation data to clarify the reasons of change in red tide species. Year-to-year variation in calculated concentration ratio of diatom to non-diatom corresponds to the variation in observed ratio of red tide days of diatom to non-diatom. Limiting nutrient of primary production is phosphate over the period. Diatom dominated from 1991 to 1993, but it was difficult for non-diatom to grow due to the limitation by physical condition. Non-diatom was able to grow because of good physical and nutrient conditions from 1994 to 1996. And diatom dominated again under the good physical condition, and phosphorus supply was not enough for non-diatom to grow from 1998 to 2000. Phosphate concentration in the lower layer of Yodo River estuary was important to the variation in red tide species in the upper layer of Yodo River estuary.

Distribution of perfluoroalkyl compounds in Osaka Bay and coastal waters of Western Japan.

Perfluoroalkyl acids (PFAAs) including perfluoroalkyl sulfonates (PFSAs) and perfluoroalkyl carboxylates (PFCAs) were analyzed in sediment samples taken from Ajifu Waterway in Osaka city, from Osaka Bay, and from Kagoshima Bay, as well as in fifteen seawater samples collected from Osaka Bay and coastal waters of Western Japan. In all sediment samples, only PFCAs were detected, and the highest concentration was determined in Ajifu Waterway, where ΣPFAA was 58990 ng kg-1 dry weight. The total concentrations of PFAAs in sea water samples ranged between the limit of quantification and 53.4 ng L-1, and perfluorohexanoic acid was the most prevalent and had the highest concentration of 37 ng L-1. The changes in the patterns and concentrations of PFAAs in Osaka Bay and coastal waters of Western Japan indicate that the PFAAs in surface waters are influenced by sources from Keihanshin Metropolitan Area, mainly the Yodo River basin, and the dilution effect which naturally occurs during their transport to the Pacific Ocean.