Major and trace elements in the surface water of Tonle Sap Lake, Mekong River, and other tributary rivers in Cambodia.

To evaluate the seasonal water circulation of Tonle Sap Lake and its tributary rivers in Cambodia, the spatial distribution patterns of major and trace elements in surface water were investigated. Based on the similarity of the dissolved elemental concentrations, the water samples were mainly divided into the three groups: samples with relatively high percentages of Ca, Mo, and Sb (Subcluster B1); samples with high Si, Al, and Fe (B2); and samples with high Na, K, and Mg (B3). During the rainy season, the elemental composition of lake water (B1) appeared to be greatly influenced by the intrusion of water from the Mekong River (B1) through the Tonle Sap River (B1). During the dry season, the type of lake water shifted to B3, suggesting that the lake water stored during the rainy season was replaced by inflow from other tributaries and groundwater in its vicinity. Thus, the seasonal changes in the elemental composition of the lake water were largely controlled by surface water and groundwater circulation. The dissolved As concentration was higher in the lake water and during the dry season than that in the river water and during the rainy season, indicating the discharge of As from the lake's bottom sediment during the dry season. Although the redox cycling of Fe and Mn appeared to be less important due to the shallow water depth in the lake, there are potential risks of As poisoning induced by the formation of an anoxic water mass and increment in the concentration of phosphorus if eutrophication continues to progress.

Strontium isotope analysis of otoliths reveals differences in the habitat salinity among three sympatric stickleback species of the genus Pungitius.

The analysis of otolith Sr isotope ratios (87Sr/86Sr) is a powerful method to study fish migration in freshwater areas. However, few studies have applied this method to study fish movement in brackish-water environments. Furthermore, despite the fact that habitat differentiation has been shown to drive genetic differentiation and reproductive isolation among stickleback fish, no studies have used the otolith 87Sr/86Sr ratios to analyze habitat differentiation between stickleback ecotypes and species. In this study, we analyzed the otolith 87Sr/86Sr ratios of three sympatric stickleback species of the genus Pungitius in the Shiomi River on Hokkaido Island, Japan: P. tymensis, the brackish-water type of the P. pungitius-P. sinensis complex, and the freshwater type of the P. pungitius-P. sinensis complex. First, we created a mixing equation to depict the relationship between habitat salinity and the 87Sr/86Sr ratios of river water. We found that the otolith 87Sr/86Sr ratios differed significantly among the three species, indicating that the three species utilize habitats with different salinities: P. tymensis and the brackish-water type inhabit freshwater and brackish-water environments, respectively, with the freshwater type using intermediate habitats. In addition, we found that some freshwater individuals moved to habitats with higher salinities as they grew. Our study demonstrates that the analysis of otolith 87Sr/86Sr ratios is a useful method for studying the habitat use of fish in brackish-water environments and habitat differentiation among closely related sympatric and parapatric species.

Microbial nitrification and acidification of lacustrine sediments deduced from the nature of a sedimentary kaolin deposit in central Japan.

Kaolin deposits in the Seto-Tono district, central Japan, were formed by intense kaolinization of lacustrine arkose sediments deposited in small and shallow inland lakes in the late Miocene. Based on mineralogical and stable isotopic (Fe, C, N) studies of Motoyama kaolin deposit in the Seto area, we concluded that it was formed by microbial nitrification and acidification of lacustrine sediments underneath an inland lake. Small amounts of Fe-Ti oxides and Fe-hydroxide in the kaolin clay indicated that iron was oxidized and leached during the kaolinization. The field occurrences indicate that leached ferric iron precipitated on the bottom of the kaolin deposit as limonite crusts, and their significantly fractionated Fe isotope compositions suggest the involvement of microbial activity. The C/N ratios of most of the kaolin clay are distinctly higher than those of modern lacustrine sediment. Although, the possibility of a low-temperature hydrothermal origin of the kaolin deposit cannot be completely ruled out, it is more likely that acidification by dilute nitric acid formed from plant-derived ammonia could have caused the kaolinization, Fe oxidation and leaching. The nitrate-dependent microbial Fe oxidation is consistent with dilute nitric acid being the predominant oxidant.

Magnesium isotopes reveal bedrock impacts on stream organisms.

Magnesium is an essential element to aquatic organisms and understanding the origin of Mg is important for understanding their growth. Ultimately, Mg in streams is derived from the chemical weathering of bedrock in the catchment. In this study, we used Mg stable isotope ratios (δ26Mg) to test whether stream organisms reflect lithological sources in stream catchments. In November 2017 and May 2018, we sampled aquatic insects and small gobies from six temperate streams in the Lake Biwa area (central Japan). Three of these streams had up to 38% limestone in their catchment (limestone streams), and three streams lacked limestone (non-limestone streams). We hypothesised that stream organisms from limestone streams had significantly lower δ26Mg values compared to those of the same organisms from non-limestone streams. Aquatic insects from limestone streams had an average of 0.78‰ lower δ26Mg values than those of the same organisms from non-limestone streams, thereby indicating a lithological control on the δ26Mg of aquatic insects. Aquatic insects often showed an offset to higher δ26Mg values compared to those of stream water, thereby pointing to a 26Mg-enriched diet as an additional Mg source to water and/or Mg isotope fractionation during Mg accumulation. Instead, stream water was the main Mg source for small gobies, as their bones reflected the δ26Mg of water. We concluded that δ26Mg could trace Mg sources of aquatic organisms, and the same methodology can be applied to other metals.

Variation of strontium stable isotope ratios and origins of strontium in Japanese vegetables and comparison with Chinese vegetables.

To evaluate the utility of 87Sr/86Sr ratio for determining the geographical provenance of vegetables, we compared 87Sr/86Sr ratios and Sr concentrations in five vegetable species grown in Japan and China, and we also examined the relationships between 87Sr/86Sr ratios in vegetables, the soil-exchangeable pool, irrigation water, and fertilizer from 20 Japanese agricultural areas. The vegetable 87Sr/86Sr ratios in Japan were similar for all species within a given agricultural area, but tended to be low in northeast Japan and high in southwest Japan. The median 87Sr/86Sr ratio in Japanese vegetables was similar to that in fertilizer, suggesting that in addition to rock-derived Sr, vegetables contain Sr derived from fertilizers. In most cases, the 87Sr/86Sr ratios for the Japanese and Chinese vegetables differed by approximately 0.710. Linear discriminant analysis using both 87Sr/86Sr and the Sr concentration allowed more accurate discrimination between vegetables from the two countries.

Characterization of a new candidate isotopic reference material for natural Pb using primary measurement method.

A lead isotopic standard solution with natural abundance has been developed by applying a mixture of a solution of enriched 208Pb and a solution of enriched 204Pb (208Pb-204Pb double spike solution) as bracketing method. The amount-of-substance ratio of 208Pb:204Pb in this solution is accurately measured by applying EDTA titrimetry, which is one of the primary measurement methods, to each enriched Pb isotope solution. Also metal impurities affecting EDTA titration and minor lead isotopes contained in each enriched Pb isotope solution are quantified by ICP-SF-MS. The amount-of-substance ratio of 208Pb:204Pb in the 208Pb-204Pb double spike solution is 0.961959 ± 0.000056 (combined standard uncertainty; k = 1). Both the measurement of lead isotope ratios in a candidate isotopic standard solution and the correction of mass discrimination in MC-ICP-MS are carried out by coupling of a bracketing method with the 208Pb-204Pb double spike solution and a thallium internal addition method, where thallium solution is added to the standard and the sample. The measured lead isotope ratios and their expanded uncertainties (k = 2) in the candidate isotopic standard solution are 18.0900 ± 0.0046 for 206Pb:204Pb, 15.6278 ± 0.0036 for 207Pb:204Pb, 38.0626 ± 0.0089 for 208Pb:204Pb, 2.104406 ± 0.00013 for 208Pb:206Pb, and 0.863888 ± 0.000036 for 207Pb:206Pb. The expanded uncertainties are about one half of the stated uncertainty for NIST SRM 981, for 208Pb:204Pb, 207Pb:204Pb and 206Pb:204Pb, or one eighth, for 208Pb:206Pb and 207Pb:206Pb, The combined uncertainty consists of the uncertainties due to lead isotope ratio measurements and the remaining time-drift effect of mass discrimination in MC-ICP-MS, which is not removed by the coupled correction method. In the measurement of 208Pb:204Pb, 207Pb:204Pb and 206Pb:204Pb, the latter contribution is two or three times larger than the former. When the coupling of a bracketing method with the 208Pb-204Pb double spike solution and a thallium internal addition method is applied to the analysis of NIST SRM 981, the measured lead isotope ratios are in good agreement with its certified values. This proves that the developed method is not only consistent with the conventional one by NIST SRM 981 but also enables measurement of the lead isotope ratios with higher precision.

A simple and rapid method for isotopic analysis of nickel, copper, and zinc in seawater using chelating extraction and anion exchange.

Stable isotope ratios of nickel, copper, and zinc are powerful tools for elucidating the biogeochemical cycling of trace metals in the ocean. However, analytical difficulties have impeded isotopic studies of these metals. We present a simple and rapid method for simultaneous analysis of Ni, Cu, and Zn isotope ratios in seawater using NOBIAS Chelate-PA1 resin and anion exchange resin. A NOBIAS Chelate-PA1 resin column was used to quantitatively collect Ni, Cu, and Zn from seawater and thoroughly remove the seawater matrix. Subsequent anion exchange purified and separated the Ni, Cu, and Zn from each other. The blanks used in this method (0.22 ng for Ni, 0.29 ng for Cu, and 0.53 ng for Zn) were sufficiently low to determine the isotope ratios of Ni, Cu, and Zn in surface seawater. Using this method, we analyzed GEOTRACES reference seawater samples (i.e., SAFe D1 and SAFe D2), National Research Council Canada certified materials (i.e., CASS-5 and NASS-6), and seawater samples collected from different depths in the subarctic South Pacific. The results were consistent with previously reported values. This method is expected to accelerate isotopic research and contribute to our understanding of biogeochemical cycling in the ocean.

Tracing the Geographical Origin of Onions by Strontium Isotope Ratio and Strontium Content.

The strontium (Sr) isotope ratio ((87)Sr/(86)Sr) and Sr content were used to trace the geographical origin of onions from Japan and other countries, including China, the United States of America, New Zealand, Australia, and Thailand. The mean (87)Sr/(86)Sr ratio and Sr content (dry weight basis) for onions from Japan were 0.70751 and 4.6 mg kg(-1), respectively, and the values for onions from the other countries were 0.71199 and 12.4 mg kg(-1), respectively. Linear discriminant analysis was performed to classify onions produced in Japan from those produced in the other countries based on the Sr data. The discriminant equation derived from linear discriminant analysis was evaluated by 10-fold cross validation. As a result, the origins of 92% of onions were correctly classified between Japan and the other countries.