Sediment Reference Materials Research Articles

Characterization of typical transuranic nuclides in a reference fallout material using SF-ICP-MS

For the quality control in determining transuranic nuclides in fallout samples, this work first reported the 237Np activity concentration in a reference fallout material and further calculated the activity ratios of 237Np/239+240Pu and 237Np/241Am, and the atom ratio of 237Np/239Pu in it. The reference fallout material prepared by the Meteorological Research Institute was collected at 14 stations throughout Japan in 1963–1979. The 237Np and Pu isotopes (239Pu and 240Pu) were separated and purified using AG MP-1M anion-exchange resin, quantified using 242Pu as an isotope dilution tracer, and determined by the SF-ICP-MS. The analytical method was validated by the analysis of 4 sediment reference materials. The activity concentrations of 237Np, 239Pu and 240Pu were (25.9 ± 0.6) × 10−3, 4.10 ± 0.01 and 2.89 ± 0.04 Bq/kg, respectively, in the investigated reference fallout material. The activity ratio of 237Np/239+240Pu (3.7 ± 0.1) × 10−3 was consistent with the global fallout evaluation value. The 237Np/239Pu atom ratio of 0.561 ± 0.014 was higher than the average global fallout value of 0.41 ± 0.010, indicating the necessity of establishing regional characteristic global fallout value of 237Np/239Pu atom ratio for assessment of radioactive contamination. Comparison of the 237Np/239+240Pu activity ratios between in the reference fallout material and in soils over several decades indicated that 237Np has stronger migration capability than Pu isotopes in soils because 237Np was depleted compared to reference fallout material.

Multi-element analysis of unfiltered samples in river water monitoring—digestion and single-run analyses of 67 elements

Routine analysis of inorganic analytes in whole water samples from rivers (unfiltered river water) is rarely reported in scientific publications. However, this sample type is valuable and often used in long-term monitoring, regulation, and catchment element budgets, as it includes the dissolved, colloidal, and particulate fraction in one sample type. Preservation measures are not needed and solid–liquid partitioning can be disregarded, which simplifies automated sampling and storage procedures. In this study, we provide several digestion protocols for whole water samples from rivers and the subsequent multi-element analysis of 67 major, minor, and trace elements: Li, Be, B, Na, Mg, Al, Si, P, S, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, Ge, As, Se, Br, Rb, Sr, Y, Zr, Nb, Mo, Ru, Ag, Cd, In, Sn, Sb, Te, Cs, Ba, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Hf, Ta, W, Ir, Pt, Au, Hg, Tl, Pb, Bi, Th, U. In the absence of whole water reference materials for inorganic analytes, we introduce simulated whole water samples by suspending sediment reference materials as quality control measures. The applicability for improved routine water quality monitoring was successfully tested on samples from different rivers revealing variations of the element fingerprints over time.Graphical abstract

Sensitive Determination of Arsenic by Photochemical Vapor Generation with Inductively Coupled Plasma Mass Spectrometry: Synergistic Effect from Antimony and Cadmium.

A novel method for the determination of trace arsenic (As) by photochemical vapor generation (PVG) with inductively coupled plasma mass spectrometry measurement was developed in this study. The synergistic effect from antimony (Sb) and cadmium (Cd) was found for the photochemical reduction of As for the first time. Effective photochemical reduction of As was obtained in the system containing 10% (v/v) acetic acid, 5.0 mg L-1 Sb(III), and 20.0 mg L-1 Cd(II) with 100 s UV irradiation. Analytical sensitivity of As(III) was comparable with that of As(V) under the tested conditions, making direct determination of total As feasible. Compared to the pneumatic nebulization method, analytical sensitivity of the developed method was enhanced about 50 folds. The PVG efficiency was estimated up to be 99 ± 3%. The limit of detection (LOD) (3σ) was found to be 2.1 ng L-1 for As, which was improved about 30-fold compared to that using direct sample introduction solution nebulization. Considering the sample dilution prior to analysis (usually one-fold), the LOD was actually enhanced about 15 folds. The relative standard deviations of seven replicate measurements of 1.0 μg L-1 As(III) and As (V) standard solutions were 2.3 and 2.9% for As(III) and As(V), respectively. The proposed method was successfully applied for the detection of As in certified reference materials of sediments (GBW07303a and GBW07305a), as well as three water samples. The mechanism of the PVG system was investigated by using gas chromatography mass spectrometry, electron paramagnetic resonance, and X-ray photoelectron spectroscopy. (CH3)3As along with (CH3)3Sb were synthesized under UV irradiation. Besides, volatile species of Cd were also found. The result obtained in this study is useful for developing efficient "sensitizers" in PVG and understanding the transformation of As in the presence of hydride/cold vapor forming elements in the photochemical process.

Analysis of PCDD/Fs in environmental samples by using gas chromatography in combination with high resolution mass spectrometry: optimization of sample preparation

ABSTRACT This study developed a simple, economical and time-saving clean-up procedure based on an in-house packed column system for the determination of the most toxic-relevant 17 PCDD (polychlorinated dibenzo-p-dioxin) and PCDF (polychlorinated dibenzofuran) congeners in environmental samples following accelerated solvent extraction. The extract solution was cleaned up using a manually packed column system consisting of a multi-layer silica gel column and an activated carbon column. After clean-up, dioxins and furans were analysed by using gas chromatography in combination with high-resolution mass spectrometry. Isotopic labelled spiking experiments investigated the recovery of all dioxin and furan congeners. Then, the clean-up procedure for environmental samples was validated by applying the analysis of both clean soil reference material (CRM EDF-5183) and heavily contaminated sediment reference material (CRM EDF-5184) samples, as well as participating in the proficiency test (PT) for sediment samples. The recovery efficiency of isotope-labelled standard compounds in certified reference material (CRM) samples and PT samples ranged from 35% to 101% and between 46.1% and 105%, respectively. The mass concentrations of 17 PCDD/Fs in CRM samples were in the acceptable range. The absolute z-score value for each PCDD/F congener in the PT samples was below 1, confirming the analytical procedure’s high accuracy. The applied clean-up procedure in this study has demonstrated accuracy, repeatability and a significant increase in sample extraction/preparation productivity by reducing the time for sample preparation.

Rapid monitoring of 241Am in small amount of sediment samples by combining extraction chromatography for highly efficient separation of interfering and matrix elements and ICP-MS/MS measurement

The analysis of 241Am in environmental samples is of great importance in the fields of geological repositories and radiation protection. The triple quadrupole inductively coupled plasma mass spectrometry (ICP-MS/MS) has a strong analytical and interference removal capability for long half-life radionuclides. In this study, the ability of ICP-MS/MS to determine ultra-trace level of 241Am in environmental samples was further explored. The instrumental sensitivity for Am detection was significantly improved (ca. 20 times) by employing an APEX-Ω high efficiency introduction system. The gases of O2 and He were introduced to the reaction cell for eliminating of interferences and Am was detected as AmO+ ions. High separation factors (>2000) of Am and Pu were obtained at proper gas flow rates by chemical resolution of the instrument. Meanwhile, the background signals caused by possible polyatomic interferences for 241Am and 243Am were sufficiently reduced. A simple and rapid chromatographic separation method for purposeful and efficient separation of 241Am from matrix and interfering elements was developed. The overall chemical recoveries were about 68% and the detection limit of 241Am for the established method was 0.18 fg g−1 (equivalent to 0.02 mBq g−1). Several marine sediment reference materials were analyzed for the validation of the method and the results showed that this method was suitable for the determination of 241Am in solid environmental samples. The method was finally applied to real marine sediment samples collected in the western North Pacific after the Fukushima nuclear accident.

Detection of trace antimony by vanadium (IV) ion assisted photochemical vapor generation with inductively coupled plasma mass spectrometry measurement

In this work, a method for sensitive detection of trace antimony (Sb) was developed by inductively coupled plasma mass spectrometry (ICP MS) coupled with photochemical vapor generation (PVG). V(IV) ions were used as new “sensitizers” for improving the PVG efficiency of Sb. Factors influenced the PVG and the detection of Sb by ICP MS were investigated, including the type and concentration of low molecular weight organic acids, the UV irradiation time, the concentration of V(IV) ions, the air-liquid interface, the flow rate of Ar carrier gas, and interferences from co-existing ions. It was found that efficient reduction of Sb was obtained in the medium of 10% (v/v) formic acid (FA), 10% (v/v) acetic acid (AA), and 80 mg L−1 of V(IV) with 100 s UV irradiation. Under the selected conditions, there was no significant difference in analytical sensitivity between Sb(III) and Sb(V). The limit of detection (LOD, 3σ) was 4.7 ng L−1 for Sb with ICP MS measurement. Compared to traditional direct solution nebulization, the analytical sensitivity obtained in this work was enhanced about 19-fold. Relative standard deviations (RSDs, n = 7) were 1.9% and 2.3% for replicate measurement of 0.5 μg L−1 Sb(III) and Sb(V) standard solutions, respectively. The proposed method was applied for the determination of trace Sb in water samples and two certified reference materials (CRMs) of sediments with satisfactory results. Moreover, the generated volatile species of Sb in this work was found to be (CH3)3Sb.

Multi-element Simultaneous sensitization of solution cathode glow discharge atomic emission spectrometry by using portable semiconductor anode refrigeration

In this study, a modified solution cathode glow discharge atomic emission spectrometry (SCGD-AES) was used to detect metal elements in electroplating sewage. The SCGD-AES device was equipped with a portable semiconductor anode refrigeration unit, which was built independently. The red-heat effect of tungsten electrode was alleviated by adding the portable refrigeration unit, thus improving thermal stability with the withstand voltage from 1040 V to 1140 V. Compared with the devices without semiconductor refrigeration, the chromium was excited more favorable when the discharge voltage increased, and the limit of detection (LOD) decreased by 8.5 times. Furthermore, the LODs of Zn, Cd, Ni, Cu and Pb decreased by 1.8–3.2 times, respectively, which realized the detection of elements in electroplating sewage and showed high performance in the field of trace elements analysis. Furthermore, the accuracy of the method was verified by stream sediment reference material (GBW07312), and the results were consistent with the certified values. The recoveries of elements added to industrial sewage and seawater range were from 90.5 to 98.7%, demonstrating good accuracy of the proposed method.

Silicon Isotope Compositions of Soil and Sediment Reference Materials Determined by MC‐ICP‐MS

This study presents a method for high‐precision Si isotope measurement of soil and sediment reference materials using multi‐collector inductively coupled plasma‐mass spectrometry with HF‐free digestion. Potential impacts on instrumental measurement, including acid concentration, Si concentration mismatch and matrix effects, were rigorously evaluated. The acidity mismatch caused a significantly negative shift in δ30Si values when the HCl concentration ratios of the sample/standard were higher than 2. The Si concentration mismatch could result in an obvious deviation in δ30Si values when the sample/standard concentration ratios are > 1.5 or < 0.7. Matrix elements in solution did not affect Si isotope measurements when Na/Si ≤ 2, Mg/Si ≤ 2, Al/Si ≤ 0.5, K/Si ≤ 2, Ca/Si ≤ 1 and Fe/Si ≤ 2. Increasing the loading volume from 1 ml to 6 ml during chemical separation can still enable effective purification of Si and is more efficient for low Si content samples. The long‐term measurement precision of three igneous rock reference materials (BHVO‐2, BCR‐2 and AGV‐2) was better than ± 0.06‰ (2s) for δ30Si values. The δ30Si values of eighteen soil and sediment reference materials were identical in two laboratories. The values varied from −1.65‰ to −0.13‰, indicating that Si isotopes can be more widely used to study supergene processes.

Species-specific isotope dilution analysis of monomethylmercury in sediment using GC/ICP-ToF-MS and comparison with ICP-Q-MS and ICP-SF-MS

A recently introduced inductively coupled plasma-time-of-flight-mass spectrometer (ICP-ToF-MS) shows enhanced sensitivity compared to previous developments and superior isotope ratio precision compared to other ToF and commonly used single-collector ICP-MS instruments. Following this fact, an improvement for isotope dilution ICP-MS using the new instrumentation has been reported. This study aimed at investigating whether this improvement also meets the requirements of species-specific isotope dilution using GC/ICP-MS, where short transient signals are recorded. The results of the analysis of monomethylmercury (MMHg) of a sediment reference material show that isotope ratio precision of ICP-MS instruments equipped with quadrupole, sector-field, and time-of-flight mass analyzers is similar within a broad range of peak signal-to-noise ratio when analyzing one isotopic system. The procedural limit of quantification (LOQ) for MMHg, expressed as mass fraction of Hg being present as MMHg, w(Hg)MMHg, was similar as well for all investigated instruments and ranged between 0.003 and 0.016 μg/kg. Due to the simultaneous detection capability, the ICP-ToF-MS might, however, be more favorable when several isotopic systems are analyzed within one measurement. In a case study, the GC/ICP-ToF-MS coupling was applied for analysis of MMHg in sediments of Finow Canal, a historic German canal heavily polluted with mercury. Mass fractions between 0.180 and 41 μg/kg (w(Hg)MMHg) for MMHg, and 0.056 and 126 mg/kg (w(Hg)total) for total mercury were found in sediment samples taken from the canal upstream and downstream of a former chemical plant.Graphical abstract

High-precision measurement of U-Pu-Np-Am concentrations and isotope ratios in environmental reference materials by mass spectrometry

We report results of precise and sensitive mass spectrometric measurements of uranium, plutonium, neptunium, and americium concentrations and isotope ratios in a variety of environmental reference materials. Most of our work has been done on NIST SRM 4350b, River Sediment, but we also present results for NIST SRM 4354, Lake Sediment; NIST SRMs 4355 and 4355a, Peruvian Soil; NIST SRM 4357, Ocean Sediment; NIST SRM 1648a, Urban Particulate Material; NIST SRM 1649b, Urban Dust; IAEA CRM 385, Ocean Sediment; USGS BCR-2, Columbia River Basalt; and USGS BHVO-2, Hawaiian Volcanic Observatory Basalt. These materials reflect a wide range in long-lived actinide concentrations (e.g. 1E4 to 1E10 atoms 239Pu/g) and isotope ratios. Measurements were performed in a clean laboratory by isotope dilution, multi-collector thermal ionization and multi-collector inductively coupled plasma mass spectrometry. In general, our results are in agreement with, but lower the uncertainty of, literature or certificate values for these reference materials. Our uranium results for the basalts also confirm previously reported high-precision mass spectrometric results from our laboratory. In many cases our measurements of U-Pu-Np-Am nuclides appear to be novel.Extensive results for NIST SRM 4350b, River Sediment, indicate that this material is heterogeneous for Pu-Np-Am concentrations and isotope ratios at a sample size of 5 g or lower. Pu–Np isotope ratios and a241Pu-241Am model age of 1954 reflect a mix of plutonium production operations at the nearby Hanford, Washington site, and global atmospheric fallout from nuclear weapons testing. Results for the oceanic sediment materials (NIST SRM 4357 and IAEA 385) collected near Sellafield, U.K. vary but are also indicative of local anthropogenic sources of varying Pu isotopic composition and a mean 241Pu-241Am model age of 1964. Large environmental fractionation between Pu and Np is observed for the ocean, river, and lake sediment reference materials. Novel measurements for the two air particulate SRMs indicate high U, Pu and Np concentrations for these collections in 1976–1977 with an anomalous regional fallout Pu isotopic signature. Results for BHVO-2 and other Hawaiian basalts indicate that those which erupted before or during the period of abundant atmospheric nuclear weapons testing (1950–1970) contain significant levels of Pu (on the order of 1E7 atoms 239Pu/g) with a global fallout Pu isotopic composition, compared to more recent eruptions which incorporated less Pu. Hence, Hawaiian basalts may provide an integrated temporal record of anthropogenic actinide fallout deposition from the atmosphere since eruption.

Determination of iodine-129 in twenty soil and sediment reference materials

129I concentrations in twenty soil and sediment certified reference materials were presented for meeting the ever-growing demands in environmental, geological and nulcear sciences, including method development, calibration and quality control, etc.

Development of Iron Speciation Reference Materials for Palaeoredox Analysis

The development and application of geochemical techniques to identify redox conditions in modern and ancient aquatic environments has intensified over recent years. Iron (Fe) speciation has emerged as one of the most widely used procedures to distinguish different redox regimes in both the water column and sediments, and is the main technique used to identify oxic, ferruginous (anoxic, Fe(II) containing) and euxinic (anoxic, sulfidic) water column conditions. However, an international sediment reference material has never been developed. This has led to concern over the consistency of results published by the many laboratories that now utilise the technique. Here, we report an interlaboratory comparison of four Fe speciation reference materials for palaeoredox analysis, which span a range of compositions and reflect deposition under different redox conditions. We provide an update of extraction techniques used in Fe speciation and assess the effects of both test portion mass, and the use of different analytical procedures, on the quantification of different Fe fractions in sedimentary rocks. While atomic absorption spectroscopy and inductively coupled plasma‐optical emission spectrometry produced comparable Fe measurements for all extraction stages, the use of ferrozine consistently underestimated Fe in the extraction step targeting mixed ferrous–ferric minerals such as magnetite. We therefore suggest that the use of ferrozine is discontinued for this Fe pool. Finally, we report the combined data of four independent Fe speciation laboratories to characterise the Fe speciation composition of the reference materials. These reference materials are available to the community to provide an essential validation of in‐house Fe speciation measurements.

The technique of high‐pressure powder pressing with polyester film covering for XRF of geochemical samples

AbstractThe method of determination of major (Si, Al, Fe, Mg, Ca, Na, K, Mn, P, Ti) and trace elements (As, Ba, Br, Ce, Cl, Co, Cr, Cu, F, Ga, Nb, Sr, La, Ni, Pb, Rb, S, U, Th, V, Y, Zn, Zr) in geochemical samples by wavelength dispersive X‐ray fluorescence spectrometer with a new sample preparation technique‐high pressure pressed pellet and covered with a 3.6 μm polyester film is proposed. The pellet was pressed at 2,000 kN, which was particularly meaningful for the sample with high silicon content and ideal pellet was formed without binder. Coating with a polyester film prevented the variation of chlorine content after multiple analyses of the same pellet, which was caused by the vacuum and long‐time irradiation. And 62 rock, soil and sediment reference materials were applied to create calibration curves. The accuracy of the method was evaluated with another eight certified reference materials that were not used in the regression curve. In most cases, the relative error between the certified value and the calculated value was <10% for major elements and <25% for trace elements, except for those approaching the limit of detection. The limit of detection obtained using this pellet preparation technology is suitable for geochemical analyses.

Determination of Mercury in Sediments by Slurry Sampling Electrothermal Atomic Absorption Spectrometry

The concentration of mercury in suspensions of sediments is determined by electrothermal atomic absorption spectrometry (ET-AAS) using a novel chemical modifier (ChM) based on activated carbon treated by iron(II) formate. The efficiency of chemical modifiers based on activated carbon, also modified by Ag(I), Au(III), Pd(II), Co(II), and Ni(II) compounds is studied. The optimum conditions are found for the temperature and time program of the atomizer; they prevent mercury losses at the stage of drying sample suspensions and also exclude spectral interferences at the stage of atomization and measurement of the analytical signals. The minimum characteristic mass of mercury (52 pg) is reached using an iron-containing chemical modifier based on activated carbon. The conditions of ET-AAS analysis using this ChM are tested on certified reference materials of sediments and a sample selected near the sea port of Temryuk (Sea of Azov). The limit of detection found by the 3s-test was 0.05 mg/kg and the relative standard deviation was 5% at the concentration of mercury in the sample 149 mg/kg.

Development and Validation of a Sector-Field Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) Method for Analyzing the Diagenesis-Designating Metals in Marine Sediments

The inductively coupled plasma – mass spectrometry (ICP-MS) technique was applied for the quantification of specific metals in marine sediments following a four-step microwave-assisted digestion protocol. The effects of microwave heating and digesting medium on metal recovery were investigated using lake and river sediment reference materials to minimize the deviations from certified values. Increasing the temperature and time variables improves the accuracy of the ICP-MS measurements so that an optimized acid-digestion protocol enables the determination of heavy metals in sediments with relative errors better than 10%. The developed method was applied to measure longitudinal metal distribution in sediments collected from the continental shelf of the East Siberian Sea in the range from 50 to 600 km. Minima in the content of redox sensitive elements such as Mn, Mo, V, U, and Sb at distances from 200 to 300 m to the coast are most likely related to diagenetic processes such as sulfide reduction in the upper part of the sediment. In addition, the quality of sediments under consideration was assessed in terms of the average and maximum concentrations of heavy metals that may contaminate the bottom seawater. The developed method can be recommended as a standard tool for accurate and precise sediment analysis with important geochemical and environmental implications.

Application potential of dummy molecularly imprinted polymers as solid-phase extraction sorbents for determination of low-mass polybrominated diphenyl ethers in soil and sediment samples

Despite the introduction of restrictive regulations in the USA and the European Union, polybrominated diphenyl ethers (PBDEs) are still found in various types of environmental and biological samples at significant concentration levels. The presence of these persistent organic pollutants in the environment raises important issues because of their negative impact on immunological and neurological systems, and on the hormonal balances in living organisms. From the analytical point of view, the final determination of PBDEs would entail substantial challenges, because it would necessitate conducting the pre-concentration of analytes, or sample clean up. The aim of the present study is to demonstrate the analytical application potential of developed dummy molecularly imprinted polymers as solid-phase extraction sorbents for the selective recognition of low-mass PBDEs. The 4,4′-dihydroxydiphenyl ether was employed as a dummy template of low-mass PBDEs. The developed types of the sorption materials were used in the sample preparation stage of the analytical procedure to determine the PBDE-47 and PBDE-99 levels in selected representatives of environmental samples—reference materials of soil and bottom sediments. The recovery values of PBDE-47 and PBDE-99 from the studied solid samples ranged from 60% to 87%, depending on the applied DMIPs type.

Validation of Total Mercury in Marine Sediment and Biological Samples, Using Cold Vapour Atomic Absorption Spectrometry

A method for the measurement of total mercury (T-Hg) in environmental samples using cold vapour atomic absorption spectrometry (CV AAS) has been validated yielding a dynamic range (0.04–10.00 μg/kg) and high certified reference material (CRM) recovery (>90%). The validation was carried out according to International Union of Pure and Applied Chemistry (IUPAC) validation and Eurachem Guides. A freeze-dried and homogenised sample was weighed and then digested using Suprapur acids (HNO3, H2SO4, and HF) with potassium dichromate solution in a hot block digestion system. A calibration curve was constructed (R2 > 0.999). Two CRMs (Marine Sediment Reference Material (PACS-3) and Trace Elements in Muscle Tissue (Trace Elements and Methylmercury in Mussel Tissue (NIST2976)) were utilised for quality assurance and control. The limit of quantification (LOQ) calculated as 0.04 µg/kg, and uncertainty (U) calculated as 2%. The obtained results showed the suitability of this method for direct mercury measurement in environmental samples. Additionally, the proficiency of this method was recognised by accreditation under the standard of International Organization for Standardization (ISO/IEC 17025:2017) for competence of testing and calibration laboratories.

Stability of organochlorine pesticides during storage in water and loaded SPE disks containing sediment

With regard to the Water Framework Directive (WFD) and the required investigation of the whole water sample including suspended particulate matter (SPM), a storage stability study was conducted to determine the suitable storage time and conditions of 21 organochlorine pesticides (OCPs) spiked in water samples and pre-concentrated on solid-phase extraction disks (SPE disks). Furthermore, this work demonstrates the behaviour of three different certified sediment reference materials (CRMs) contaminated with OCPs in water samples as well as loaded on SPE disks under different temperature conditions and storage time periods. Extracts collected on SPE disks were stored for 3, 14 and 30 days at both 4 °C and −18 °C in darkness covered in (a) freezer bags and (b) aluminum foil. With few exceptions the results of these tests demonstrate stability of OCPs up to 30 days at −18 °C. The recoveries for most substances range between 84% and 133%. Furthermore, the stability of OCPs in water samples additionally spiked with CRM up to 500 mg and stored at a temperature of 4 °C in darkness up to 56 days was investigated. The addition of sodium azide enhanced the stability of some substances during storage, especially the endosulfans (I, II) but most substances were stable regardless of sodium azide addition over the entire storage period. An important conclusion of this study is that the storage of loaded SPE disks is an appropriate alternative to storing water samples.

Determination of ultra-low level plutonium isotopes (239Pu, 240Pu) in environmental samples with high uranium

In order to measure trace plutonium and its isotopes ratio (240Pu/239Pu) in environmental samples with a high uranium, an analytical method was developed using radiochemical separation for separation of plutonium from matrix and interfering elements including most of uranium and ICP-MS for measurement of plutonium isotopes. A novel measurement method was established for extensively removing the isobaric interference from uranium (238U1H and 238UH2+) and tailing of 238U, but significantly improving the measurement sensitivity of plutonium isotopes by employing NH3/He as collision/reaction cell gases and MS/MS system in the triple quadrupole ICP-MS instrument. The results show that removal efficiency of uranium interference was improved by more than 15 times, and the sensitivity of plutonium isotopes was increased by a factor of more than 3 compared to the conventional ICP-MS. The mechanism on the effective suppress of 238U interference for 239Pu measurement using NH3-He reaction gases was explored to be the formation of UNH+ and UNH2+ in the reactions of UH+ and U+ with NH3, while no reaction between NH3 and Pu+. The detection limits of this method were estimated to be 0.55 fg mL-1 for 239Pu, 0.09 fg mL−1 for 240Pu. The analytical precision and accuracy of the method for Pu isotopes concentration and 240Pu/239Pu atomic ratio were evaluated by analysis of sediment reference materials (IAEA-385 and IAEA-412) with different levels of plutonium and uranium. The developed method were successfully applied to determine 239Pu and 240Pu concentrations and 240Pu/239Pu atomic ratios in soil samples collected in coastal areas of eastern China.

A Rapid Acid Digestion Technique for the Simultaneous Determination of Bromine and Iodine in Fifty‐Three Chinese Soils and Sediments by ICP‐MS

Bromine and iodine are important tracers for geochemical and environmental studies. In this study, a rapid acid digestion (HNO3 + HF) with ammonia dilution for the simultaneous determination of bromine and iodine in soils and sediments using ICP‐MS was developed. The recoveries of Br and I were controlled by the synergic effect of temperature and time. It took only 15 min at 140 °C for the complete recovery of Br and I in sediment (GSD‐2) and soil (GSS‐24) reference materials, which is a process that needs 2–6 h at 90 °C. A serious loss of Br and I was found at a higher digestion temperature of 190 °C. A 5% v/v NH4OH dilution effectively eliminated the memory effects and stabilised the signals of Br and I. Moreover, ammonia dilution also avoided the corrosiveness of HF on the sample introduction system and torch of ICP‐MS. Tellurium is a more suitable internal standard element than In in the ammonia medium. To avoid the adsorption of residues of dissolution on Te, addition of Te should be carried out after centrifuging the solution. The developed method was successfully applied to determine Br and I in fifty‐three Chinese soil and sediment reference materials. This simple method shows great potential for the rapid determination of Br and I in large batches of geological and environmental samples commonly analysed for mineral exploration and environmental geochemistry studies.