Seawater Reference Material Research Articles

Autocalibration based on dilution of a single concentrated standard is used for the determination of silicate in sea water by the modified molybdenum blue method

The silicate (Si) molybdenum blue method was modified by combining oxalate and ascorbic acid into a single reagent and was used for determining Si in sea water samples. The first step of this automated assay protocol was designed to perform either a calibration by a single Si standard prepared in deionized (DI) water, or to dilute samples in the range of 0–160 μM Si to fit into 0–20 μM Si calibration range using a 20 cm flow cell. By designing the assay protocol to function in batch mode, the influence of salinity on calibration was eliminated, thus making the method suitable for analysis of samples collected in the open ocean, coastal areas, or rivers. Reproducibility and accuracy of this method were evaluated by analysis of certified sea water reference materials. Phosphate (P) does not interfere significantly if the Si:P ratio is 4:1 or larger. The limit of detection was 514 nM Si, r.s.d. 2.1 %, sampling frequency 40 s/h, reagent consumption 700 μL/sample, and using deionized water as the carrier solution.

Determination of 90Sr in highly radioactive aqueous samples via conversion to a kinetically stable 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid complex followed by concentration–separation–fractionation based on capillary electrophoresis–liquid scintillation

BackgroundThe Fukushima Daiichi Nuclear Power Plant accident (2011) released large amounts of radioactive substances into the environment and generated highly radioactive debris. Post-accident countermeasures are currently in the phase of fuel debris removal, which requires the analysis of radioactive contaminants in the environment and fuel. The spectra of solely β-emitting nuclides, such as 90Sr, overlap; thus, an effective method for nuclide separation is desired. Since conventional methods for high-dose sample analysis pose substantial exposure risks and generate large amounts of secondary radioactive waste, faster procedures allowing for decreased radiation emission are highly desirable. ResultsIn this study, we developed a 90Sr2+ quantitation technique based on liquid scintillation counting (LSC)–coupled capillary transient isotachophoresis (ctITP), along with two-point detection and relying on the rapid concentration, separation, and fractionation of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA)-complexed 90Sr2+ in a single run. The applicability of our method for the analysis of real-world samples was verified by conducting addition-recovery experiments using a seawater reference material and radioactive liquid waste obtained from the radioactive waste treatment facility at the Japan Atomic Energy Agency. The recovery determined by LSC was 95–113%, indicating successful quantitative analysis. 90Sr recovery was determined to be 90.1% from a contaminated water sample obtained from the Fukushima Daiichi Nuclear Power Plant, which was analyzed using the standard addition of 90Sr. The sensitivity (detection limit = 0.016 Bq) of the proposed method on a radioactivity basis was equal to or higher than that of the conventional method using ion exchange-LSC (0.012–0.07 Bq). Significance and noveltyOur method allows for the handling of high-dose radioactive samples at the microliter level and is substantially faster than conventional ion exchange protocols, whereas ctITP has not been used for practical applications due to inaccurate collection and lack of a suitable chemical system. The concentration–separation–fractionation protocol in ctITP is successful due to the existence of a rare inert Sr2+ complex and precise fractionation. This study establishes a pathway toward safer and more practical analysis of radionuclides.

Rubidium Isotope Ratios of International Geological Reference Materials

In this study we determined rubidium isotope ratios in twenty‐one commonly used international geological reference materials, including igneous, sedimentary and metamorphic rocks, as well as an IAPSO seawater reference material. All δ87Rb results were obtained relative to the NIST SRM 984 reference material. For most reference materials, Rb was purified using a single column loaded with Sr‐spec resin. For reference materials containing low Rb but high mass fractions of matrix elements (such as basic rock and seawater), Rb was purified using two‐column chromatography, with the first column packed with AGMP‐50 resin and the second column packed with Sr‐spec resin. Two methods for instrumental mass bias correction, sample‐standard bracketing (SSB) mode, and the combined sample‐standard bracketing and Zr internal normalisation (C‐SSBIN) method, were compared for Rb isotopic measurements by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS). The long‐term reproducibility of Rb isotopic measurements using both methods was similar, better than 0.06‰ (2s, standard deviation) for NIST SRM 984. Significant Rb isotopic fractionation was observed among the reference materials, with an overall variation in δ87Rb values of approximately 0.5‰. The δ87Rb values of igneous rocks ranged from ‐0.28‰ to +0.06‰, showing a trend from heavier isotopic compositions in mafic rocks to lighter δ87Rb values in the more evolved felsic rocks. The sedimentary and metamorphic rocks had Rb isotope ratios similar to those of igneous rocks. The δ87Rb values of the reference materials related to low‐temperature geological processes showed a wider range than those of high‐temperature processes. Notably, the IAPSO seawater reference material had a δ87Rb value of +0.14‰, which deviated from that of igneous rocks, and represents the heaviest reservoir of Rb isotopes found thus far on Earth. The comprehensive dataset presented here has the potential to serve for quality assurance purposes, and provide a framework for interlaboratory comparisons of Rb isotope ratios.

Determination of uranium isotopes in marine sediments and seawaters by SF ICP-MS after rapid chemical separation using TK200 resin.

This work provided a novel analytical procedure for rapid and precise uranium isotopic determination in marine sediment and seawater, using a new type of extraction resin, TK200 resin, in combination with microwave digestion (for marine sediments), Fe(OH)3 co-precipitation (for seawater), and single collector sector field-inductively coupled plasma mass spectrometry (SF ICP-MS) measurement. The removal ability of TK200 extraction chromatography for the interfering elements (IEs) Hg, Pb, Th, Pt, Tl, and the matrix rare earth elements (REEs) was carefully investigated. High decontamination factors (DFs) were obtained for IEs and REEs. Accurate quantification of uranium isotope ratios was accomplished based on a "double-cycle" ICP-MS measurement method. The analytical method was optimized and validated with isotopic standards (IRMM-187), matrix-containing certified reference marine sediments (IAEA-384, IAEA-385, and IAEA-412), and seawater reference material (IAEA-443). A stable chemical recovery of ~ 90% was obtained for both types of marine environmental samples, and the method showed great efficiency with a total analytical time of less than 6h. The proposed procedure was validated following ISO/IEC 17025 guidelines. The important factors affecting the isotope ratio results (instrument background, procedural blank, memory effects, peak tailing, mass discrimination, dead time, and hydride interferences) were considered in the estimation of combined uncertainties. This work provides an alternative way for the determination of trace uranium isotope ratios and can be applied in the emergency monitoring of nuclear accidents and marine environmental analysis.

Collision course; high-precision mass-independent and mass-dependent calcium isotope measurements using the prototype collision cell MC-ICPMS/MS, Proteus

This paper reports measurements of mass-independent and mass-dependent Ca isotope variations using the prototype collision cell MC-ICPMS/MS, Proteus. Helium and hydrogen gases are introduced into the collision cell and the well characterised resonant charge exchange and proton transfer reactions between Ar+ ions and H2 molecules results in almost complete removal of the 40Ar+ ions allowing the measurement of the 40Ca isotope by MC-ICPMS without resorting to ‘cold’ plasma.A range of reference materials have been characterised for both their mass-independent and mass-dependent Ca isotope compositions relative to the international reference material NIST SRM 915a. Notably, the radiogenic 40Ca/44Ca isotope ratio (internally normalised to 42Ca/44Ca) can be accurately measured with typical reproducibility better than 40 ppm (pooled 2 SD) for a single measurement using 12 μg of Ca. Reference materials USGS GSP‐2 and CRPG FKN have notably radiogenic 40Ca/44Ca, with values of 434 ± 7 and 5513 ± 17 ppm respectively relative to NIST SRM 915a (pooled 2 SE, n = 35 and 5 respectively). In contrast, multiple repeat measurements of mantle derived reference materials BIR, BHVO-2, BCR-2 and JP-1 yield values that are slightly unradiogenic (mean − 23 ± 5 ppm, pooled 2 SE, n = 71) relative to NIST SRM 915a, bone ash and seawater reference materials, likely reflecting crustal components in the latter. Coupled measurements of the minor 48Ca and 43Ca isotopes give 48Ca/44Ca and 43Ca/44Ca (internally normalised to 42Ca/44Ca) with typical reproducibilities of ± 40 and ± 16 ppm respectively (pooled 2 SD) for single (24 μg Ca) analyses. Multiple repeats yield mean values for terrestrial reference materials that are within their pooled 2 SE uncertainties of SRM 915a, to precisions of ± 15 and ± 6 ppm respectively. Measurements of mass-dependent Ca isotope variations (δ44/40Ca) have been made using a 42Ca-43Ca double spike isotope tracer together with measurements of 40Ca and 44Ca and have typical reproducibilities of ± 0.035 ‰ (pooled 2 SD) for single (12 μg) analyses. Measured δ44/40Ca values for reference materials are within uncertainty of previously reported values. Moreover, given that the double spike inversion uses the same isotopes as the mass independent determinations of 40Ca/44Ca and 43Ca/44Ca, our documentation of the absence of anomalies at a precision of better than 20 ppm in a range of low K/Ca terrestrial reference materials implies that the accuracy of our δ44/40Ca analyses is at this level of uncertainty.

Determination of Ultratrace Level 135Cs and 135Cs/137Cs Ratio in Small Volume Seawater by Chemical Separation and Thermal Ionization Mass Spectrometry.

The atomic ratio of 135Cs/137Cs is a powerful fingerprint for distinguishing the source terms of radioactive contamination and tracing the circulation of water masses in the ocean. However, the determination of the 135Cs/137Cs ratio is very difficult due to the ultratrace level of 135Cs (<0.02 mBq/m3) and 137Cs (<2 Bq/m3) in the ordinary seawater samples. In this work, a sensitive method was developed for determination of 135Cs concentration and 135Cs/137Cs ratio in seawater using chemical separation combined with thermal ionization mass spectrometry (TIMS) measurement. Cesium was first preconcentrated from seawater using ammonium molybdophosphate-polyacrylonitrile column chromatography and then purified using cation exchange chromatography to remove the interferences. With this method, decontamination factors of 6.0 × 106 for barium and 1800 for rubidium and a chemical yield of more than 60% for cesium were achieved. By using glucose as an activator, the ionization efficiency of cesium was significantly improved to 50.6%, and a constant high current of Cs+ (20 V) can be maintained for more than 180 min, which ensures sensitive and reliable measurement of low level 135Cs and 137Cs. Detection limits of 4.0 × 10-17 g/L for both 135Cs and 137Cs for 200 mL seawater were achieved, which enables the accurate determination of 135Cs concentration and 135Cs/137Cs ratio in a small volume of seawater samples (<200 mL). The developed method has been validated by analysis of seawater reference material IAEA-443. Seawater samples collected from the Greenland Sea, Baltic Sea, and Danish Straits have been successfully analyzed for 135Cs concentrations and 135Cs/137Cs ratios, and the results showed that 135Cs concentrations in the seawater of the Baltic Sea is much higher than that in the Greenland Sea, which is attributed to the high deposition of Chernobyl accident derived radiocesium in the Baltic Sea region.

Determination of Copper and Cadmium in Petroleum Produced Formation Water by Electrothermal Atomic Absorption Spectrometry after Cloud Point Extraction

Cloud point extraction (CPE) in association with graphite furnace atomic absorption spectrometry (GF AAS) was proposed for preconcentration and quantification of trace amounts of copper and cadmium in samples of saline produced formation water from petroleum exploration. The procedure was based on the formation of hydrophobic complexes of the analytes with 1,5-diphenylthiocarbazone (dithizone) in a micellar media of the surfactant (1,1,3,3-tetramethyl butyl) phenyl-polyethylene glycol (Triton X-114). Constrained mixture design was performed for the optimization of the proportions of the three solutions employed in the CPE: Triton X-114, dithizone, and buffer solution. Under the recommended conditions, the CPE GF AAS procedure allowed to obtain enrichment factors of 18 and 11 times, limits of quantification of 0.030 and 0.12 µg L-1 and precision, expressed as relative standard deviation (RSD, n = 8, 2.0 µg L-1), of 1.1 and 4.3% for copper and cadmium, respectively. The CPE GF AAS method was applied to the determination of copper and cadmium in samples of saline produced formation water from petroleum exploration, and its accuracy was accessed by analyzing certified reference material CASS-5 (Nearshore Seawater Reference Material for Trace Metals) from National Research Council (Canada).

Cadmium(II) determination in production waters from petroleum exploration after its separation from the highly saline matrix mediated by a semipermeable membrane device

This paper reports the development of a novel approach for the separation of Cd(II) from production waters generated during petroleum prospection. The analyte was separated from the highly saline waters as a dithiocarbamate (DDTC) complex using a low-density polyethylene semipermeable membrane device (SPMD) filled with chloroform. The quantification of cadmium(II) in the extracts was performed by graphite furnace atomic absorption spectrometry (GF AAS). Several parameters that could affect the performance of the SPMD (pH of the sample, concentration of DDTC, type and volume of solvent used to fill the device, and extraction time) were evaluated in order to achieve maximum transference of Cd(II) and sensitivity. Under the best conditions, the SPMD was filled with 3.0 mL of CHCl3 and used to extract Cd(II) (as Cd(DDTC)2 complex) from a solution containing 3.75 × 10−4 mol L−1 of sodium dithiocarbamate at pH = 9.0. The SPMD was maintained in contact, under shaking, with the sample solution for 90 min. After that, the inner solvent containing the extracted Cd was collected and diluted to 5.0 mL with ethanol prior to analyte quantification by GF AAS. External calibration was possible using Cd(II) standard solutions prepared in a 10% (m/v) NaCl medium. The limits of detection and quantification of the method were 0.08 and 0.24 µg L−1, respectively. The method was employed for the quantification of Cd(II) in four samples of real production waters with high salinity and in a certified reference material of seawater (MX014, from National Measurement Institute of Australia). Recovery tests were also performed by spiking the samples Cd(II), resulting in the recovery percentages in the range of 90 – 132%.

Ultratrace Pb determination in seawater by solution-cathode glow discharge-atomic emission spectrometry coupled with hydride generation

A novel method for the determination of ultratrace Pb in seawater by solution-cathode glow discharge atomic emission spectrometry (SCGD-AES) coupled with hydride generation (HG) has been developed. In the SCGD process, the hollow Ti tube, which can introduce gas instead of a solid tungsten rod is used as a discharge anode and combined with hydride generator. HG technology can not only separate Pb from a seawater matrix and reduce the matrix interference on detection, but can also significantly improve the transfer and atomization efficiencies for SCGD-AES. The optimum working conditions for HG and SCGD-AES for quantitative analysis of Pb were determined as 1% H2C2O4 as the masking agent and addition of 3% formic acid to increase Pb volatilization. The limit of detection (LOD) for Pb was decreased by two orders of magnitude in comparison to the SCGD-AES process alone. Under optimal conditions, the LOD for Pb was 0.17 μg L−1, and the relative standard deviation was 2.1% (n = 11) for 100 μg L−1 Pb in artificial seawater. The proposed quantification method was verified using a seawater reference material (BWQ7001-2016), and the obtained results agreed well with certified values. Finally, the approach was used to quantitatively analyse Pb in seawater, and the results agreed well with those obtained by inductively coupled plasma mass spectrometry. The recoveries of standard addition were between 96.0% and 103.0%.

Ultratrace Determination of 99Tc in Small Natural Water Samples by Accelerator Mass Spectrometry with the Gas-Filled Analyzing Magnet System.

In the frame of studies on the safe disposal of nuclear waste, there is a great interest for understanding the migration behavior of 99Tc. 99Tc originating from nuclear energy production and global fallout shows environmental levels down to 107 atoms/g of soil (∼2 fg/g). Extremely low concentrations are also expected in groundwater after diffusion of 99Tc through the bentonite constituting the technical barrier for nuclear waste disposal. The main limitation to the sensitivity of the mass spectrometric analysis of 99Tc is the background of its stable isobar 99Ru. For ultratrace analysis, the Accelerator Mass Spectrometry (AMS) setup of the Technical University of Munich using a Gas-Filled Analyzing Magnet System (GAMS) and a 14 MV Tandem accelerator is greatly effective in suppressing this interference. In the present study, the GAMS setup is used for the analysis of 99Tc in samples of the seawater reference material IAEA-443, a peat bog lake, and groundwater from an experiment of in situ diffusion through bentonite in the controlled zone of the Grimsel Test Site (GTS) within the Colloid Formation and Migration (CFM) project. With an adapted chemical preparation procedure, measurements of 99Tc concentrations at the fg/g levels with a sensitivity down to 0.5 fg are accomplished in notably small natural water samples. The access to these low concentration levels allows for the long-term monitoring of in situ tracer tests over several years and for the determination of environmental levels of 99Tc in small samples.

Determination of ultra-trace level of 232Th in seawater by ICP-SFMS after matrix separation and preconcentration

This article describes the development and validation of an analytical procedure for the matrix separation, preconcentration and determination of sub-ng kg−1 levels 232Th in a small volume (20 mL) of seawater samples. The matrix separation and Th preconcentration was carried out using a commercially available ion-chelation system seaFAST-pico. The acidified to pH < 2 seawater samples were mixed on-line with the ammonium acetate buffer (pH of 6.0 ± 0.2) before loading on the column containing resin with iminodiacetic and ethylenediaminetriacetic functional groups. At this pH, 232Th was quantitatively retained on the resin, demonstrating a good affinity (selectivity) for Th in seawater matrix. The element retained on the resin was eluted using only 0.2 mL of 1.8 M HNO3 enabling to achieve high preconcentration factor. The pretreatment procedure, with two sample loading cycles (each one 10 mL), was accomplished in about 25 min. Determining 232Th mass fraction in seawater samples was based on isotope dilution inductively coupled plasma mass spectrometry (ID ICP-MS) method, which was considered as the most accurate calibration strategy for precise quantification of 232Th mass fraction in seawater samples. ISO/IEC17025 and Eurachem guidelines were followed to perform the validation of the developed in this study procedure. In the case of seawater samples with natural level of thorium the major contributions to the expanded uncertainty arose from the uncertainty associated with isotopic ratio measurements in the isotopically spiked sample, followed by the correction for procedural blank and the correction for mass discrimination effect. The estimated method detection limit for 232Th was 0.005 ng kg−1. The developed method was successfully applied to the determination of 232Th mass fraction in seawater reference samples: IAEA-443, SLEW-3, NASS-4, NASS-6, and CASS-5. Although 232Th is not certified in any of the seawater reference materials, a good agreement was obtained between the results in this study and data published elsewhere.

Stable carbon isotopes of dissolved inorganic carbon for a zonal transect across the subpolar North Atlantic Ocean in summer 2014

Abstract. The stable carbon isotope composition of dissolved inorganic carbon (δ13CDIC) in seawater was measured in samples collected during June–July 2014 in the subpolar North Atlantic. Sample collection was carried out on the RRS James Clark Ross cruise JR302, part of the “Radiatively Active Gases from the North Atlantic Region and Climate Change” (RAGNARoCC) research programme. The observed δ13CDIC values for cruise JR302 fall in a range from −0.07 to +1.95 ‰, relative to the Vienna Pee Dee Belemnite standard. From duplicate samples collected during the cruise, the 1σ precision for the 341 results is 0.08 ‰, which is similar to our previous work and other studies of this kind. We also performed a cross-over analysis using nearby historical δ13CDIC data, which indicated that there were no significant systematic offsets between our measurements and previously published results. We also included seawater reference material (RM) produced by A. G. Dickson (Scripps Institution of Oceanography, USA) in every batch of analysis, enabling us to improve upon the calibration and quality-control procedures from a previous study. The δ13CDIC is consistent within each RM batch, although its value is not certified. We report δ13CDIC values of 1.15 ± 0.03 ‰ and 1.27 ± 0.05 ‰ for batches 141 and 144 respectively. Our JR302 δ13CDIC data can be used – along with measurements of other biogeochemical variables – to constrain the processes that control DIC in the interior ocean, in particular the oceanic uptake of anthropogenic carbon dioxide and the biological carbon pump. Our δ13CDIC results are available from the British Oceanographic Data Centre – doi:10.5285/22235f1a-b7f3-687f-e053-6c86abc0c8a6.

전 세계 대양 영양염 자료의 상호 비교성 향상을 위한 국제동향 : SCOR Working Group 147 (Towards Comparability of Global Oceanic Nutrient Data, COMPONUT) 활동에 대하여

To understand the fluctuation of global carbon levels caused by the biogeochemical cycle within the ocean interior, it is essential to achieve comparability of global oceanic nutrient data to a fairly high degree. The Scientific Committee on Ocean Research (SCOR) commissioned a working group (WG147) to establish a system for achieving comparability of oceanic nutrient data within 1% among laboratories around the world. The introduction of international activities for improving nutrient comparability will facilitate the use of nutrient reference material of seawater by researchers within Korea, which will help in meeting international standards of nutrient comparability and promote international cooperation.

An inter-laboratory comparison assessing the quality of seawater carbon dioxide measurements

Seawater CO2 measurements are being made with increasing frequency as interest grows in the ocean's response to changing atmospheric CO2 levels and to climate change. The ultimate usefulness of these measurements depends on the data quality and consistency. An inter-laboratory comparison was undertaken to help evaluate and understand the current reliability of seawater CO2 measurements. Two seawater test samples of different CO2 content were prepared according to the usual method for the creation of seawater reference materials in the Dickson Laboratory at Scripps Institution of Oceanography. These two test samples were distributed in duplicate to more than 60 laboratories around the world. The laboratories returned their measurement results for one or more of the following parameters: total alkalinity (AT), total dissolved inorganic carbon (CT), and pH, together with information about the methods used and the expected uncertainty of the measurements. The majority of laboratories reported AT and CT values for all their measurements that were within 10μmolkg−1 of the assigned values (i.e. within ±0.5%), however few achieved results within 2μmolkg−1 (i.e. within ±0.1%), especially for CT. Results for the analysis of pH were quite scattered, with little suggestion of a consensus value. The high-CO2 test sample produced results for both CT and pH that suggested in many cases that CO2 was lost during analysis of these parameters. This study thus documents the current quality of seawater CO2 measurements in the various participating laboratories, and helps provide a better understanding of the likely magnitude of uncertainties in these measurements within the marine science community at the present time. Further improvements will necessarily hinge on adoption of an improved level of training in both measurement technique and of suitable quality control procedures for these measurements.

A Robust Procedure for High‐Precision Determination of Rare Earth Element Concentrations in Seawater

This study reports a robust procedure that permits precise measurement of all fourteen naturally occurring rare earth element (REE) concentrations, present at ng kg−1 to sub ng kg−1 levels, in ~ 100 ml seawater. This procedure is simple and can be routinely applied to measure seawater REEs with relatively high sample throughput. The procedure involves addition of a 142Ce‐145Nd‐171Yb‐enriched spike mixture, iron co‐precipitation, REE purification with chromatographic separation and the use of a magnetic‐sector‐field ICP‐MS (Element 2) coupled with a desolvating sample introduction system (Aridus 1). Critical steps of the procedure, including co‐precipitation pH and matrix removal, have been optimised through a set of experiments described here. The accuracy of the new procedure was assessed against a gravimetric mixture of REEs, and the precision was demonstrated by repeated measurement of two well‐mixed natural seawaters. Repeated analyses of these seawater reference materials (RMs), using ~ 100 ml seawater for each aliquot, indicate precision of 3% (1s) for the REEs. Measured REE concentrations of two uncertified seawater RMs (CASS‐4 and NASS‐5) are consistent with published values, and REE concentrations of the GEOTRACES intercalibration samples show good agreement with those reported by other participant laboratories. REE concentrations for other intercalibration samples (SAFe and Arctic PS70) are also reported.

Determination of Zr, Nb, Mo, Sn, Hf, Ta, and W in seawater by N-benzoyl-N-phenylhydroxylamine extraction chromatographic resin and inductively coupled plasma-mass spectrometry

A method has been developed for the determination of zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), molybdenum (Mo), tungsten (W), and tin (Sn) in seawater by quadrupole inductively coupled plasma-mass spectrometry (Q-ICP-MS). The method is based on separation of the seven elements by extraction chromatography using N-benzoyl-N-phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin. The optimized procedure indicates that the BPHA resin has high selective adsorption for Zr, Nb, Mo, Sn, Hf, Ta, and W (known as fluoride soluble elements), whereas other interference and matrix elements are minimally adsorbed. The optimized eluent mixture with their molarity gives satisfactory recoveries for all analytes. The recovery can be achieved 99% for Zr, 97% for Nb, 97% for Mo, 99% for Sn, 99% for Hf, 95% for Ta, and 98% for W, respectively, by eluting with 6mL of 6molL−1 HF/1molL−1 HCl. Furthermore, the technique for separation and enrichment of these elements provides a low total method blank. The detection limits for this method are 0.5ppt for Zr, 0.2ppt for Nb, 1.7ppt for Mo, 1.0ppt for Sn, 0.1ppt for Hf, 0.1ppt for Ta, and 0.3ppt for W, respectively. The validity of the method is evaluated by replicate analyses of seawater reference materials; the precision of the results is better than 3% (RSD, n=4), and the results are in good agreement with certified values. The established procedure has proved to be both practical and effective for seawater sample analyses.

Calcium, Na, K and Mg Concentrations in Seawater by Inductively Coupled Plasma‐Atomic Emission Spectrometry: Applications to IAPSO Seawater Reference Material, Hydrothermal Fluids and Synthetic Seawater Solutions

We report a measurement procedure to determine simultaneously the major cation concentrations (Na, Ca, K and Mg) of seawater‐derived solutions by inductively coupled plasma‐atomic emission spectrometry. The best results were obtained when the IAPSO (‘standard’) seawater reference material was diluted by thirty times with Milli‐Q® water. We obtained an average reference value rK (the ratio of the mass fraction of potassium to that of chlorine, i.e., (g kg−1)/(g kg−1)) for IAPSO seawater of 0.0205 ± 0.0006 (2.9% RSD), not significantly different from 0.0206 ± 0.0005 (2.4% RSD) for seawater composition reported in the literature. The measured Na, Ca and Mg concentrations correspond to rNa, rCa and rMg values of 0.5406 ± 0.0026 (0.5% RSD), 0.02192 ± 0.00048 (2.2% RSD) and 0.06830 ± 0.00047 (0.7% RSD), respectively, in line with previous values measured by wet‐chemistry and atomic absorption spectrophotometry or wet‐chemical titration. Our measurement procedure was used successfully on synthetic seawater solutions and high‐temperature hydrothermal fluids.

Ultra-trace plutonium determination in small volume seawater by sector field inductively coupled plasma mass spectrometry with application to Fukushima seawater samples

Long-term monitoring of Pu isotopes in seawater is required for assessing Pu contamination in the marine environment from the Fukushima Dai-ichi Nuclear Power Plant accident. In this study, we established an accurate and precise analytical method based on anion-exchange chromatography and SF-ICP-MS. This method was able to determine Pu isotopes in seawater samples with small volumes (20–60L). The U decontamination factor was 3×107–1×108, which provided sufficient removal of interfering U from the seawater samples. The estimated limits of detection for 239Pu and 240Pu were 0.11fgmL−1 and 0.08fgmL−1, respectively, which corresponded to 0.01mBqm−3 for 239Pu and 0.03mBqm−3 for 240Pu when a 20L volume of seawater was measured. We achieved good precision (2.9%) and accuracy (0.8%) for measurement of the 240Pu/239Pu atom ratio in the standard Pu solution with a 239Pu concentration of 11fgmL−1 and 240Pu concentration of 2.7fgmL−1. Seawater reference materials were used for the method validation and both the 239+240Pu activities and 240Pu/239Pu atom ratios agreed well with the expected values. Surface and bottom seawater samples collected off Fukushima in the western North Pacific since March 2011 were analyzed. Our results suggested that there was no significant variation of the Pu distribution in seawater in the investigated areas compared to the distribution before the accident.

Measurement of the Isotopic Composition of Molybdenum in Geological Samples by MC‐ICP‐MS using a Novel Chromatographic Extraction Technique

A novel preconcentration method is presented for the determination of Mo isotope ratios by multi‐collector inductively coupled plasma‐mass spectrometry (MC‐ICP‐MS) in geological samples. The method is based on the separation of Mo by extraction chromatography using N‐benzoyl‐N‐phenylhydroxylamine (BPHA) supported on a microporous acrylic ester polymeric resin (Amberlite CG‐71). By optimising the procedure, Mo could be simply and effectively separated from virtually all matrix elements with a single pass through a small volume of BPHA resin (0.5 ml). This technique for separation and enrichment of Mo is characterised by high selectivity, column efficiency and recovery (~ 100%), and low total procedural blank (~ 0.18 ng). A 100Mo‐97Mo double spike was mixed with samples before digestion and column separation, which enabled natural mass‐dependent isotopic fractionation to be determined with a measurement reproducibility of &lt; 0.09‰ (δ98/95Mo, 2s) by MC‐ICP‐MS. The mean δ98/95MoSRM 3134 (NIST SRM 3134 Mo reference material; Lot No. 891307) composition of the IAPSO seawater reference material measured in this study was 2.00 ± 0.03‰ (2s, n = 3), which is consistent with previously published values. The described procedure facilitated efficient and rapid Mo isotopic determination in various types of geological samples.

Improved accuracy of determination of dissolved silicate in seawater using absorption spectrometry

We studied to develop a certified reference material of seawater for nutrient analysis whose relative combined standard uncertainty for dissolved silicate was <0.5 %. In order to precisely measure the content of dissolved silicate in seawater, widely used absorption spectrometry with the so-called molybdenum blue was investigated as one of the highly sensitive determination methods. For the absorption spectrometry, a batch mode and a continuous flow analysis (CFA) mode were used and the characteristics of the calibration curves in the both modes were examined in detail. The calibration curve in the batch mode could be explained by a first-order regression line, whereas that in the CFA mode fitted to a second-order regression line. Therefore, for measuring the silicate content of seawater whose matrix depends on its origin, a standard addition method in a batch mode is preferable, though strict control of the compositions of the solutions for the standard addition calibration curve are greatly important for getting good linearity of the curve. In addition, in the case of the standard addition method, it is important to measure the blank value including the background; in the present study, the origins related to the blank were discussed and evaluated. The relative combined standard uncertainty of 0.48 % could be achieved for the measurement of content of 28 μmol/kg silicate in seawater, providing that the volume ratio between each of the molybdenum blue colorimetric reagents and the seawater was kept constant among all the solutions for the standard addition calibration curve. The procedure was validated using artificial seawater with a known concentration of silicate. Such highly improved precision and trueness which reaches the recent target of the community related to analysis of nutrients in seawater is reported for the first time. The developed procedure will provide a good way of validation for the analysts who need measurement with high precision and trueness on the content of silicate in seawater and other samples.