Determination of ultra-trace Te species in open ocean waters based on Mg(OH)2 coprecipitation, anion exchange resin column separation and inductively coupled plasma sector-field mass spectrometry using a 125Te-enriched isotope spike.

We present a method for the determination of ultra-trace Te species (Te(IV) and Te(VI)) in open ocean waters. The proposed method is based on Mg(OH)2 coprecipitation, anion exchange resin column separation and inductively coupled plasma sector-field mass spectrometry (ICPSFMS) using a 125Te-enriched isotope spike. The largest advantage of the method is that the use of the spike allows accurate and precise determination when it combines with either isotope dilution or recovery correction. Tellurium-IV and VI are preconcentrated in a Mg(OH)2 precipitate and separated mutually by an anion exchange resin column. Te(IV) is retained to the column, while Te(VI) passing through the column is recovered by a subsequent column procedure after reduction of Te(VI) to Te(IV). Te(IV) is successfully eluted with a small amount of 0.01 M HCl. The additional merit of using this eluent is elimination of components that result in a memory effect during the measurement of Te(IV). Possible mass spectral interference on Te(IV) can be excluded by adjusting the mass window, and the Te(IV) concentrations determined by this approach agree well with those independently obtained by an oxidation procedure which removes the interference. The accuracy of the proposed method is verified with homemade standard seawater for which the measured concentrations agree well with results calculated from the value of the standard solution. Procedural blanks for Te(IV) and Te(VI) are 1.5 ± 0.9 pg kg-1 (n = 11) and 1.3 ± 0.9 pg kg-1 (n = 11) with corresponding overall detection limits of 3.0 pg kg-1 and 2.8 pg kg-1, respectively. Using the method, we have clarified vertical profiles of Te(IV) and Te(VI) in the subarctic western North Pacific for the first time.

Determination of Nd isotopic composition in seawater using newly developed solid phase extraction and MC-ICP-MS.

Determination of neodymium (Nd) isotopic composition in seawater is useful for tracing water masses and geochemical cycles for lithogenic elements in the ocean. A new separation procedure for determination of the Nd isotopic composition of in seawater samples was developed that offers enhanced sample throughput and improved measurement reliability. The procedure consists of conventional Fe hydroxide coprecipitation, solid phase extraction using DGA chelating resin column chromatography, and Ln Resin column chromatography to preconcentrate samples. High selectivity in HNO3 medium and elution by low concentration HCl medium for Nd are characteristics of extraction using DGA Resin®, and they allowed an evaporation step to be omitted between the chromatographic steps. These chromatographic steps, using DGA Resin to separate REEs and Ln Resin® to remove Sm, were refined from a previous study. The procedural blank value of Nd was obtained as 2 pg (n = 6) from 3 L of water samples. Chemical yield of Nd from 3 L of seawater ranged within 90-95%. The developed procedure was combined with multiple collector-ICP-MS and applied to analysis of vertical seawater samples obtained from the western subarctic gyre of the North Pacific Ocean, where εNd ranged from -1.29 ± 0.42 at the surface to -3.80 ± 0.41 at 4000 m depth. These results were validated by comparing them with results obtained by the conventional method verified in the GEOTRACES inter-calibration program.

Distinct profiles of size-fractionated iron-binding ligands between the eastern and western subarctic Pacific.

Iron (Fe) is well known as a limiting factor to control primary productivity especially in high-nutrient and low chlorophyll area such as the subarctic Pacific. The solubility of Fe is believed to be controlled by its complexation with natural organic ligands, while the distribution of organic ligands is poorly understood. Here, we report that dissolved (< 0.2 µm) organic ligands were unevenly distributed between the western and eastern stations in the subarctic Pacific. The concentration of dissolved organic ligands around the lower part of subarctic Pacific intermediate water was higher in the western station, suggesting that Fe complexation with these organic ligands supports a lateral transport within the water mass. However, a more detailed size-fractionated treatment indicated no significant difference in the soluble (< 1000 kDa) ligands' distribution between the western and eastern stations. These results suggest that organic and inorganic colloid formations are potentially essential for Fe transport mechanisms in the subarctic Pacific.

Subpolar marginal seas fuel the North Pacific through the intermediate water at the termination of the global ocean circulation.

The mechanism by which nutrients in the deep ocean are uplifted to maintain nutrient-rich surface waters in the subarctic Pacific has not been properly described. The iron (Fe) supply processes that control biological production in the nutrient-rich waters are also still under debate. Here, we report the processes that determine the chemical properties of intermediate water and the uplift of Fe and nutrients to the main thermocline, which eventually maintains surface biological productivity. Extremely nutrient-rich water is pooled in intermediate water (26.8 to 27.6 σθ) in the western subarctic area, especially in the Bering Sea basin. Increases of two to four orders in the upward turbulent fluxes of nutrients were observed around the marginal sea island chains, indicating that nutrients are uplifted to the surface and are returned to the subarctic intermediate nutrient pool as sinking particles through the biological production and microbial degradation of organic substances. This nutrient circulation coupled with the dissolved Fe in upper-intermediate water (26.6 to 27.0 σθ) derived from the Okhotsk Sea evidently constructs an area that has one of the largest biological CO2 drawdowns in the world ocean. These results highlight the pivotal roles of the marginal seas and the formation of intermediate water at the end of the ocean conveyor belt.

Shelf humic substances as carriers for basin-scale iron transport in the North Pacific.

Iron is one of the key elements controlling phytoplankton growth in large areas of the global ocean. Aeolian dust has traditionally been considered the major external source of iron in the North Pacific. Recent studies have indicated that sedimentary iron from the shelf region of the Sea of Okhotsk has a strong impact on the iron distribution in the North Pacific, while the mechanism supporting its long-distance transport remains poorly understood. Here, we report that refractory shelf humic substances, which complex and carry dissolved iron, are transported conservatively at least 4000 km from the shallow sediments of the Sea of Okhotsk to the subtropical North Pacific with the circulation of intermediate water. This result indicates that shelf humic substances are probably one of the key factors shaping the distribution of dissolved iron in the ocean interior.

Spatiotemporal variations of platinum in seawater in Otsuchi Bay, Japan after the 2011 tsunami.

Huge tsunami waves devastated coastal areas on the Pacific Ocean side of northern Japan on March 11, 2011, and seriously damaged these coastal environments. Since the tsunami, we have not yet obtained data on the present state of and changes in trace metal concentrations in seawater in these areas. Platinum (Pt), one of the rarest elements in the Earth's crust, is now widely used in a range of products, such as catalytic converters in automobiles and anticancer drugs. Increasing use and dispersal of Pt has the potential to affect aquatic environments, although Pt concentrations in open ocean seawater have been found to be very low (approximately 0.2 pmol/L). In this study, we reveal the Pt concentrations in seawater and sediment in Otsuchi Bay after the tsunami, and evaluate the behavior of the Pt. The concentrations of dissolved Pt in seawater are 0.40-1.99 pmol/L and those in river water are below the detection limit of 0.015 pmol/L. Comparing the Pt concentrations in May, higher concentrations were obtained in 2013 than in 2012, especially in the deepest seawater. The total Pt concentrations in sediment samples were 0.46-14.4 ng/g in Otsuchi Bay. Using a sequential leaching technique on the sediments, Pt concentrations in the acetic-acid fractions were 0.19-1.13 ng/g, and those in the acetic acid + hydrochloric acid hydroxylamine fractions were less than 0.03-0.71 ng/g. Seasonal variations in dissolved Pt concentrations reflected changes in the water mass structure. During the stratification season, vertical profiles indicated that Pt concentrations tended to increase with depth due to supply from the sediments, whereas in winter, the water mass was vertically well mixed. The Pt was supplied to the bottom of the water from the sediments, probably due to loosely adsorbed Pt on sediment particles being remobilized during post-depositional processes. The increased internal input of Pt within Otsuchi Bay can be explained by the release of 1.3-5.6% of the leachable fraction from sediments, probably transported from the land by the tsunami, during the water residence time in the bay.

Observation of Dispersion in the Japanese Coastal Area of Released 90Sr, 134Cs, and 137Cs from the Fukushima Daiichi Nuclear Power Plant to the Sea in 2013.

The March 2011 earthquake and tsunami resulted in significant damage to the Fukushima Daiichi Nuclear Power Plant (FDNPP) and the subsequent release of radionuclides into the ocean. Here, we investigated the spatial distribution of strontium-90 (90Sr) and cesium-134/cesium-137 (134, 137Cs) in surface seawater of the coastal region near the FDNPP. In the coastal region, 90Sr activity was high, from 0.89 to 29.13 mBq L-1, with detectable FDNPP site-derived 134Cs. This indicated that release of 90Sr from the power plant was ongoing even in May 2013, as was that of 134Cs and 137Cs. 90Sr activities measured at open ocean sites corresponded to background derived from atmospheric nuclear weapons testing fallout. The FDNPP site-derived 90Sr/137Cs activity ratios in seawater were much higher than those in the direct discharge event in March 2011, in river input, and in seabed sediment; those ratios showed large variability, ranging from 0.16 to 0.64 despite a short sampling period. This FDNPP site-derived 90Sr/137Cs activity ratio suggests that these radionuclides were mainly derived from stagnant water in the reactor and turbine buildings of the FDNPP, while a different source with a low 90Sr/137Cs ratio could contribute to and produce the temporal variability of the 90Sr/137Cs ratio in coastal water. We estimated the release rate of 90Sr from the power plant as 9.6 ± 6.1 GBq day-1 in May 2013 on the basis of the relationship between 90Sr and 137Cs activity (90Sr/137Cs = 0.66 ± 0.05) and 137Cs release rate.

Colorimetric Detection of Mercury(II) Ion in Aqueous Solution Using Silver Nanoparticles.

Novel green-chemistry synthesis of silver nanoparticles (AgNPs) is introduced as a low-cost, rapid and easy-to-use analytical method for mercury ion detection. Aqueous fruit extract of water apple (Syzygium aqueum) was used for the first time as bioreductant to synthesize stable AgNPs. The prepared AgNPs have a yellowish-brown color with a surface plasmon resonance peak at 420 nm. The addition of Hg(II) ions then changes the AgNPs color to colorless. The color change was in proportion to the concentration of Hg(II) ions. The presence of other metal ions in the system was also evaluated. The proposed method shows good selectivity and sensitivity towards Hg(II) ions. Using UV-visible spectrophotometry, the detection limit of the developed method was 8.5 × 10-7 M. The proposed method has been successfully applied for determination of Hg(II) ions in tap and lake water samples with precision better than 5%.

Dissolved Platinum Concentrations in Coastal Seawater: Boso to Sanriku Areas, Japan.

Platinum, one of the rarest elements in the earth's crust, is now widely used in a range of products, such as catalytic converters in automobiles and anticancer drugs. Increasing use and dispersal of platinum has the potential to affect aquatic environments. Platinum concentrations in open ocean seawater have been found to be very low (approximately 0.2 pmol/L); however, Pt distributions and biogeochemical cycles in coastal areas are unknown. In this study, we investigated Pt concentrations in coastal waters between the Boso and Sanriku areas, Japan, after the 2011 tsunami. We determined sub-picomolar levels of dissolved Pt using isotope-dilution Inductively coupled plasma mass spectrometry after column preconcentration with an anion exchange resin. Dissolved Pt concentrations were found to be in the range 0.20-1.5 pmol/L, with the highest concentration in bottom water of the Boso coastal area, and at stations close to Tokyo Bay. Assuming thermodynamical equilibrium, Pt was determined to be present in the form PtCl5(OH)2-, even in low-oxygen coastal waters. Vertical profiles indicated Pt levels increased toward seafloors near coastal stations and were similar to those of the open ocean at trench stations. High concentrations of dissolved Pt are thought to be derived from coastal sediments.

Determination of strontium-90 from direct separation of yttrium-90 by solid phase extraction using DGA Resin for seawater monitoring.

It is important for public safety to monitor strontium-90 in aquatic environments in the vicinity of nuclear related facilities. Strontium-90 concentrations in seawater exceeding the background level have been observed in accidents of nuclear facilities. However, the analytical procedure for measuring strontium-90 in seawater is highly demanding. Here we show a simple and high throughput analytical technique for the determination of strontium-90 in seawater samples using a direct yttrium-90 separation. The DGA Resin is used to determine the abundance of strontium-90 by detecting yttrium-90 decay (beta-emission) in secular equilibrium. The DGA Resin can selectively collect yttrium-90 and remove naturally occurring radionuclides such as (40)K, (210)Pb, (214)Bi, (238)U, and (232)Th and anthropogenic radionuclides such as (140)Ba, and (140)La. Through a sample separation procedure, a high chemical yield of yttrium-90 was achieved at 95.5±2.3%. The result of IAEA-443 certified seawater analysis (107.7±3.4 mBq kg(-1)) was in good agreement with the certified value (110±5 mBq kg(-1)). By developed method, we can finish analyzing 8 samples per day after achieving secular equilibrium, which is a reasonably fast throughput in actual seawater monitoring. By processing 3 L of seawater sample and applying a counting time of 20 h, minimum detectable activity can be as low as 1.5 mBq kg(-1), which could be applied to monitoring for the contaminated marine environment. Reproducibility was found to be 3.4% according to 10 independent analyses of natural seawater samples from the vicinity of the Fukushima Daiichi Nuclear Power Plant in September 2013.

Determination of picomolar beryllium levels in seawater with inductively coupled plasma mass spectrometry following silica-gel preconcentration.

A robust and rapid method for the determination of natural levels of beryllium (Be) in seawater was developed to facilitate mapping Be concentrations in the ocean. A solid-phase extraction method using a silica gel column was applied for preconcentration and purification of Be in seawater prior to determination of Be concentrations with inductively coupled plasma mass spectrometry (ICP-MS). Be was quantitatively adsorbed onto silica gel from solutions with pH values ranging from 6.3 to 9, including natural seawater. The chelating agent ethylenediamine tetraacetic acid was used to remove other ions in the seawater matrix (Na, Mg, and Ca) that interfere with the ICP-MS analysis. The reproducibility of the method was 3% based on triplicate analyses of natural seawater samples, and the detection limit was 0.4 pmol kg(-1) for 250 mL of seawater, which is sufficient for the analysis of seawater in the open ocean. The method was then used to determine the vertical profile of Be in the eastern North Pacific Ocean, which was found to be a recycled-type profile in which the Be concentration increased with depth from the surface (7.2 pmol kg(-1) at <200 m) to deep water (29.2 pmol kg(-1) from 3500 m to the bottom).

Recent distribution of lead in the Indian Ocean reflects the impact of regional emissions.

Humans have injected lead (Pb) massively into the earth surface environment in a temporally and spatially evolving pattern. A significant fraction is transported by the atmosphere into the surface ocean where we can observe its transport by ocean currents and sinking particles. This study of the Indian Ocean documents high Pb concentrations in the northern and tropical surface waters and extremely low Pb levels in the deep water. North of 20°S, dissolved Pb concentrations decrease from 42 to 82 pmol/kg in surface waters to 1.5-3.3 pmol/kg in deep waters. South of 20°S, surface water Pb concentrations decrease from 21 pmol/kg at 31°S to 7 pmol/kg at 62°S. This surface Pb concentration gradient reflects a southward decrease in anthropogenic Pb emissions. The upper waters of the north and central Indian Ocean have high Pb concentrations resulting from recent regional rapid industrialization and a late phase-out of leaded gasoline, and these concentrations are now higher than currently seen in the central North Pacific and North Atlantic oceans. The Antarctic sector of the Indian Ocean shows very low concentrations due to limited regional anthropogenic Pb emissions, high scavenging rates, and rapid vertical mixing, but Pb still occurs at higher levels than would have existed centuries ago. Penetration of Pb into the northern and central Indian Ocean thermocline waters is minimized by limited ventilation. Pb concentrations in the deep Indian Ocean are comparable to the other oceans at the same latitude, and deep waters of the central Indian Ocean match the lowest observed oceanic Pb concentrations.

Laterally spreading iron, humic-like dissolved organic matter and nutrients in cold, dense subsurface water of the Arctic Ocean.

The location and magnitude of oceanic iron sources remain uncertain owing to a scarcity of data, particularly in the Arctic Ocean. The formation of cold, dense water in the subsurface layer of the western Arctic Ocean is a key process in the lateral transport of iron, macronutrients, and other chemical constituents. Here, we present iron, humic-like fluorescent dissolved organic matter, and nutrient concentration data in waters above the continental slope and shelf and along two transects across the shelf-basin interface in the western Arctic Ocean. We detected high concentrations in shelf bottom waters and in a plume that extended in the subsurface cold dense water of the halocline layer in slope and basin regions. At σθ = 26.5, dissolved Fe, humic-like fluorescence intensity, and nutrient maxima coincided with N* minima (large negative values of N* indicate significant denitrification within shelf sediments). These results suggest that these constituents are supplied from the shelf sediments and then transported laterally to basin regions. Humic dissolved organic matter probably plays the most important role in the subsurface maxima and lateral transport of dissolved Fe in the halocline layer as natural Fe-binding organic ligand.

Rapid collection of iron hydroxide for determination of Th isotopes in seawater.

This work introduces a novel method of recovery of iron hydroxide using a DIAION CR-20 chelating resin column to determine Th isotopes in seawater with a sector field (SF) inductively coupled plasma mass spectrometer (ICP-MS). Thorium isotopes in seawater were co-precipitated with iron hydroxide, and this precipitate was sent to chelating resin column. Ferric ions in the iron hydroxide were bonded to functional groups of the chelating resin directly, resulting in a pH increase of the effluent by release of hydroxide ion from the iron hydroxide. The co-precipitated thorium isotopes were quantitatively collected within the column, which indicated that thorium was retained on the iron hydroxide remaining on the chelating column. The chelating column quantitatively collected (232)Th with iron hydroxide in seawater at flow rates of 20-25 mL min(-1). Based on this flow rate, a 5 L sample was processed within 3-4 h. The >20 h aging of iron hydroxide tends to reduce the recovery of (232)Th. The rapid collection method was successfully applied to the determination of (230)Th and (232)Th in open-ocean seawater samples.

Tritium in Japanese precipitation following the March 2011 Fukushima Daiichi Nuclear Plant accident.

Tritium concentrations in Japanese precipitation samples collected after the March 2011 accident at the Fukushima Dai-ichi Nuclear Power Plant (FNPP1) were measured. Values exceeding the pre-accident background were detected at three out of seven localities (Tsukuba, Kashiwa and Hongo) southwest of the FNPP1 at distances varying between 170 and 220 km from the source. The highest tritium content was found in the first rainfall in Tsukuba after the accident; however concentrations were 500 times less than the regulatory limit for tritium in drinking water. Tritium concentrations decreased steadily and rapidly with time, becoming indistinguishable from the pre-accident values within five weeks. The atmospheric tritium activities in the vicinity of the FNPP1 during the earliest stage of the accident was estimated to be 1.5×10(3) Bq/m(3), which is potentially capable of producing rainwater exceeding the regulatory limit, but only in the immediate vicinity of the source.

Unique elution behavior of bromide and nitrate in anion-exchange chromatography using aqueous potassium chloride eluent containing cadmium or zinc ion.

In anion-exchange chromatography using a high-concentration eluent and high-capacity ion-exchange resin, the effect of the countercation contained in the eluent was investigated. Cadmium(II) and zinc(II) ions were examined as additives in an aqueous potassium chloride eluent. The addition of these cations resulted in a reversed elution order of bromide and nitrate, as compared with conventional anion-exchange chromatography. The separation factor for these two anions increased as the cadmium concentration in the eluent was increased. Zinc(II) ion was also effective, but a relatively high concentration was necessary.

Equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) for sensitive, high-resolution measurement of dimethyl sulfide dissolved in seawater.

We developed an equilibrator inlet-proton transfer reaction-mass spectrometry (EI-PTR-MS) method for fast detection of dimethyl sulfide (DMS) dissolved in seawater. Dissolved DMS extracted by bubbling pure nitrogen through the sample was continuously directed to the PTR-MS instrument. The equilibration of DMS between seawater and the carrier gas, and the response time of the system, were evaluated in the laboratory. DMS reached equilibrium with an overall response time of 1 min. The detection limit (50 pmol L(-1) at 5 s integration) was sufficient for detection of DMS concentrations in the open ocean. The EI-PTR-MS instrument was deployed during a research cruise in the western North Pacific Ocean. Comparison of the EI-PTR-MS results with results obtained by means of membrane tube equilibrator-gas chromatography/mass spectrometry agreed reasonably well on average (R(2) = 0.99). EI-PTR-MS captured temporal variations of dissolved DMS concentrations, including elevated peaks associated with patches of high biogenic activity. These results demonstrate that the EI-PTR-MS technique was effective for highly time-resolved measurements of DMS in the open ocean. Further measurements will improve our understanding of the biogeochemical mechanisms of the production, consumption, and distribution of DMS on the ocean surface and, hence, the air-sea flux of DMS, which is a climatically important species.

Onboard determination of submicromolar nitrate in seawater by anion-exchange chromatography with lithium chloride eluent.

Ion-exchange chromatography using a high-capacity anion exchanger with UV detection was applied to the determination of nitrate in seawater. Major ions in seawater samples did not affect the peak shape and the retention time of the nitrate when an alkaline metal cation-chloride solution was used as an eluent at high concentrations (0.5-2 mol/l). At a wavelength of 220 nm, the peak of bromide was very small because of low absorption, while its separation from the nitrate peak was good at high concentrations. Among the eluents tested, lithium chloride gave the best separation of nitrate from bromide. It was estimated that the lithium ion had the least potential for ion-pair formation with nitrate, and its retention time was prolonged compared with the retention times when using other cations; with bromide and nitrite, such an effect was not observed. The results of shipboard seawater nitrate determination by our method in the South Pacific Ocean and Antarctic Sea showed good agreement with those by the conventional photometric method using continuous flow.

Determination of picomolar levels of platinum in estuarine waters: a comparison of cathodic stripping voltammetry and isotope dilution-inductively coupled plasma mass spectrometry.

A comparative study to determine picomolar concentrations of platinum in natural waters was performed using two different analytical techniques. Results obtained by cathodic stripping voltammetry (CSV) were compared with those obtained by isotope dilution-inductively coupled plasma mass spectrometry (ID-ICPMS) combined with anion exchange resin column extraction method. Using successive UV irradiations with low-pressure mercury (L-Hg) lamp for 4h prior to CSV analysis, the results of both methods were comparable. Without adequate photolytic decomposition, the results obtained using CSV were generally lower than those obtained using ID-ICPMS in the estuarine waters around Tokyo Bay. This difference implies the presence of organically complexed Pt species in the estuarine waters. The Pt enrichment in the middle of the Tokyo Bay estuaries probably reflects the anthropogenic release of Pt from highly populated areas in Tokyo.

Shipboard analysis of picomolar levels of manganese in seawater by chelating resin concentration and chemiluminescence detection.

A new shipboard analytical method for determining picomolar levels of manganese in seawater has been developed. The method is based on a combination of chelating resin column extraction and improved chemiluminescence (CL) detection in a closed flow system. In this method, manganese in sample solution is selectively collected on newly-developed iminodiacetate-immobilized chelating resin, and then eluted with acidic solution containing hydrogen peroxide. The resulting eluent is mixed with luminol solution and aqueous ammonia after removal of iron ions by a chelating resin column, and then the mixture is introduced into the CL cell. The manganese concentration is obtained from the CL intensity. The detection limit (3SD) of manganese is 5 pmol L(-1) from 9 mL of seawater sample. The method was applied to seawater samples collected at the Okinawa Trough.