Liquid waveguide spectrophotometric measurements of arsenate and particulate arsenic, as well as phosphate and particulate phosphorus, in seawater

Sensitive methods for the determination of arsenate and particulate arsenic (PAs), as well as phosphate and particulate phosphorus (PP), in seawater are described. The method for arsenate and phosphate was established by applying automated liquid waveguide spectrophotometry. Because the reaction time for the formation of arsenate-molybdate complex is longer than that for phosphate-molybdate complex, a long Teflon tube submerged in a heating bath was installed in the conventional phosphate flow system. The arsenate was quantified as the difference between absorbances of molybdenum blue dyes with (only phosphate) and without (phosphate + arsenate) arsenate reduction treatment. Contamination was observed in the reagent for arsenate reduction and must be corrected. Linear dynamic ranges up to 1000 nM were confirmed for arsenate and phosphate. The detection limits for arsenate and phosphate were 5 and 4 nM, respectively. Freezing was a reliable sample preservation technique for both arsenate and phosphate. The method for PAs and PP was established by combining conventional persulfate oxidation of PP and the automated liquid waveguide spectrophotometry of arsenate and phosphate. The digestion efficiencies of organic As analogs were >93%. Contamination in the glass fiber filter was negligible. Field tests confirmed that the coefficients of variation (CVs) of 10–19 nM arsenate and 4–151 nM phosphate were 7–20% and 1–25%, respectively, while the CVs of 0.9 nM PAs and 10.2 nM PP were 11 % and 4 %, respectively

Sensitive determination of total particulate phosphorus and particulate inorganic phosphorus in seawater using liquid waveguide spectrophotometry

Determining the total particulate phosphorus (TPP) and particulate inorganic phosphorus (PIP) in oligotrophic oceanic water generally requires the filtration of a large amount of water sample. This paper describes methods that require small filtration volumes for determining the TPP and PIP concentrations. The methods were devised by validating or improving conventional sample processing and by applying highly sensitive liquid waveguide spectrophotometry to the measurements of oxidized or acid-extracted phosphate from TPP and PIP, respectively. The oxidation of TPP was performed by a chemical wet oxidation method using 3% potassium persulfate. The acid extraction of PIP was initially carried out based on the conventional extraction methodology, which requires 1 M HCl, followed by the procedure for decreasing acidity. While the conventional procedure for acid removal requires a ten-fold dilution of the 1 M HCl extract with purified water, the improved procedure proposed in this study uses 8 M NaOH solution for neutralizing 1 M HCl extract in order to reduce the dilution effect. An experiment for comparing the absorbances of the phosphate standard dissolved in 0.1 M HCl and of that dissolved in a neutralized solution [1 M HCl : 8 M NaOH = 8:1 (v:v)] exhibited a higher absorbance in the neutralized solution. This indicated that the improved procedure completely removed the acid effect, which reduces the sensitivity of the phosphate measurement. Application to an ultraoligotrophic water sample showed that the TPP concentration in a 1075 mL-filtered sample was 8.4 nM with a coefficient of variation (CV) of 4.3% and the PIP concentration in a 2300 mL-filtered sample was 1.3 nM with a CV of 6.1%. Based on the detection limit (3 nM) of the sensitive phosphate measurement and the ambient TPP and PIP concentrations of the ultraoligotrophic water, the minimum filtration volumes required for the detection of TPP and PIP were estimated to be 15 and 52 mL, respectively

Reconstruction of radiocesium levels in sediment off Fukushima: Simulation analysis of bioavailability using parameters derived from observed 137Cs concentrations

Radiocesium was released to the North Pacific coastal waters by the accident at the Fukushima Dai-ichi Nuclear Power Plant (1FNPP) of the Tokyo Electric Power Company (TEPCO) in March 2011. Since the radiocesium in the sediment off Fukushima was suggested as a possible source for the transfer of this radionuclide through the benthic food chain, we conducted numerical simulations of 137Cs in sediments off the Fukushima coast by using a model which incorporates dynamic transfer processes between seawater and the labile and refractory fractions in sediment particles. This model reproduced the measured temporal changes of 137Cs concentration in seabed surface sediment off Fukusima coasts, by normalizing the radiocsium transfer between seawater and sediment according to the particle diameter sizes. We found that the 137Cs level in sediment decreased by desorption during the first several months after the accident, followed by a reduction in the labile fraction until the end of 2012. The apparent decrease of the total radiocesium level in surface sediment was estimated to occur at rates of approximately 0.2 y−1 within a 20 km distance from the 1FNPP. The comparison of 137Cs level decreases in the demersal fish and the simulated temporal labile fraction in fine sediment demonstrated that the consideration of radiocesium transfer via sediment is important for determining the 137Cs depuration mechanism in some demersal fish

Biogeochemical controls of surface ocean phosphate

Surface ocean phosphate is commonly below the standard analytical detection limits, leading to an incomplete picture of the global variation and biogeochemical role of phosphate. A global compilation of phosphate measured using high-sensitivity methods revealed several previously unrecognized low-phosphate areas and clear regional differences. Both observational climatologies and Earth system models (ESMs) systematically overestimated surface phosphate. Furthermore, ESMs misrepresented the relationships between phosphate, phytoplankton biomass, and primary productivity. Atmospheric iron input and nitrogen fixation are known important controls on surface phosphate, but model simulations showed that differences in the iron-to-macronutrient ratio in the vertical nutrient supply and surface lateral transport are additional drivers of phosphate concentrations. Our study demonstrates the importance of accurately quantifying nutrients for understanding the regulation of ocean ecosystems and biogeochemistry now and under future climate conditions

Soot-containing particles over the Antarctic Ocean and the South Indian Ocean

第2回極域科学シンポジウム　共通セッション「海氷圏の生物地球化学」 11月16日（水） 統計数理研究所 3階リフレッシュフロ

The origin and characteristics of dissolved organic carbon in the highly urbanized coastal waters of Tokyo Bay

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