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1.
Mar Pollut Bull ; 193: 115082, 2023 Aug.
Article in English | MEDLINE | ID: mdl-37352799

ABSTRACT

Huge amount of trace metals emitted through manmade activities are carried by the Changjiang River into the East China Sea. Most of them deposit in the Changjiang River Estuary and threaten the regional aquatic environment. In this study, major and trace elements of 34 archive surface sediments and two cores are examined. Sequential extraction procedures were also performed on surface sediments from 12 sites. We found that Tl, Tm, Er show distinct accumulation in surface sediments in the order of Tm > Tl > Er. Particularly, abnormally elevated HREE are observed mainly in those sites near the mouth of the estuary. Most elements exhibit an obvious reduction in the upper 30 cm of core B8, reflecting a decrease of sediment discharge from Changjiang River runoff. The increase of some trace elements recorded in the upper 20 cm of core C3 demonstrates a distinct local anthropogenic input in recent years.


Subject(s)
Metals, Rare Earth , Trace Elements , Water Pollutants, Chemical , Trace Elements/analysis , Rivers , Estuaries , Water Pollutants, Chemical/analysis , Environmental Monitoring/methods , Metals, Rare Earth/analysis , China , Geologic Sediments
2.
Mar Pollut Bull ; 178: 113580, 2022 May.
Article in English | MEDLINE | ID: mdl-35366548

ABSTRACT

Industrial and commercial port activities are widely recognized worldwide as an important source of pollution to proximal estuaries. In this study, we analysed geochemical and sedimentological parameters including major and trace elements, organic matter and sediment texture in surface sediments from the estuarine environment of Southampton Water, U.K. Using these data, and multivariate statistical tools [correlation, factor and cluster analysis and pollution indices such as Enrichment Factor (EF), Pollution Load Index (PLI) and the Adverse Effect Index (AEI)], we examine sedimentary trace metal and metalloid contamination, contamination sources, and potential biological impacts of the contamination present. The geochemical data, multivariate statistical analysis and pollution indices indicate that the spatial distribution of trace metals and metalloids is influenced by both sediment composition (and mixing) and anthropogenic activities. Most trace metal and metalloid concentrations are close to local geological background levels, except for Cu, Zn and Pb. The spatial distribution of these elements indicates that the Exxon oil refinery, Southampton port, local marinas and runoff from domestic and industrial activities act effectively as point sources of these elements. Pollution indices calculations highlight a degraded environment as a result of these pollutants, and further work is needed to assess the current impact of trace metals and metalloids on local ecology.


Subject(s)
Metalloids , Metals, Heavy , Trace Elements , Water Pollutants, Chemical , Environmental Monitoring , Geologic Sediments/chemistry , Metalloids/analysis , Metals, Heavy/analysis , Trace Elements/analysis , Water/analysis , Water Pollutants, Chemical/analysis
3.
Appl Radiat Isot ; 179: 109995, 2022 Jan.
Article in English | MEDLINE | ID: mdl-34753088

ABSTRACT

A compact dual zone, two work-tube, vertical tube furnace system (Raddec Pyrolyser-Mini) has been designed for the determination of H-3 and C-14 in decommissioning wastes. An optimised methodology was developed following improvements to sample holder and bubbler trap design, sample loading and loading temperature, as well as length and style of heating programmes. A significant efficiency enhancement was obtained through 'hot-loading' of the sample into the furnace at 600 °C before finally ramping to 900 °C. Direct trapping of H-3 and C-14 in a scintillation vial located in a special anti-suck-back bubbler further improved operations, leading to a reduction in analysis time and measurement sensitivity. Co-trapping of the analytes and dual-label liquid scintillation counting also proved effective. Overall, the developed methodology led to a reduced analyte extraction/trapping time of 150 min whilst achieving limits of detection of <1 Bq/g. Validation of the procedure was assessed using a range of spiked matrices relevant to nuclear site decommissioning, reference materials and operationally-exposed materials. The compact size of this thermal extraction system is such that it allows for deployment in fume cupboards, gloveboxes and a mobile laboratory.

4.
Analyst ; 146(12): 4049-4065, 2021 Jun 14.
Article in English | MEDLINE | ID: mdl-34047735

ABSTRACT

A numerical simulation method has been developed to describe the transfer of analytes between solid and aqueous phases and assessed for a commercially available extraction chromatography resin (UTEVA resin). The method employs an ordinary differential equation solver within the LabVIEW visual programming language. The method was initially developed to describe a closed batch system. The differential equations and kinetic rate constants determined under these conditions were then applied to the flow-through column geometry. This was achieved by modelling the resin bed as a series of discrete vertically stacked sections, thereby generating an array of solid and aqueous concentration values. Axial flow was simulated by the advancement of the aqueous phase values by one array position with the value advancing from the final array position representing the column output concentration. An investigation into the observed difference in breakthrough profiles obtained under repeated conditions revealed the relative tolerance of the numerical simulation method to errors in each input parameter. Additional physical processes such as backpressure and leaching of the extractant were considered as an explanation for observed inconsistencies between experimental and simulated datasets. An elution sequence featuring multiple eluents was also simulated, demonstrating that the prediction of analyte separation sequences is possible. The potential to develop the LabVIEW coding into user friendly software with an extendable kinetic database is also discussed. This software will be a useful tool to radiochemists particularly in the development of new analytical methods using automated separation systems.

5.
Water Res ; 189: 116610, 2021 Feb 01.
Article in English | MEDLINE | ID: mdl-33278720

ABSTRACT

The environmental occurrence, fate and ecotoxicity of emerging contaminants (ECs) has been the subject of increasing research, policy and public concern over the past two decades. While a wide range of publications have examined the environmental persistence and sediment/soil interactions of ECs following their discharge into aquatic environments, the extent to which ECs are sequestered in estuarine sediments, and the impact of this on their environmental persistence and supply to the ocean, in comparison remains unclear. This Article examines the environmental concentrations of seven, relatively water-soluble and environmentally mobile, ECs (including pharmaceuticals, perfluoroalkyl compounds, and plasticisers) in dated intertidal saltmarsh cores from two contrasting estuarine sites in the southern U.K. (one heavily urbanised/industrial, the other non-urbanised). Mean sediment EC concentrations are similar in both estuarine systems (in the range 0.1 (acetaminophen) to 17 (4-hydroxyacetophenone) ng/g dry weight). Despite their variable reported Log Kow values (from ca. 0.5 to > 7), the ECs are all apparently mobile in the marsh systems studied, and where subsurface concentration maxima are present these most likely relate to local flushing or diffusive processes and cannot be clearly linked to likely input trends or changes in sediment geochemistry (including sedimentary organic carbon content). The "estuarine filter" here, at least with respect to intertidal saltmarsh sediments, shows reduced potential to sequester the seven ECs examined and mediate their supply to coastal and shelf environments.


Subject(s)
Fluorocarbons , Pharmaceutical Preparations , Water Pollutants, Chemical , Environmental Monitoring , Geologic Sediments , Water Pollutants, Chemical/analysis
6.
Proc Natl Acad Sci U S A ; 117(16): 8813-8819, 2020 04 21.
Article in English | MEDLINE | ID: mdl-32253300

ABSTRACT

The timing of human colonization of East Polynesia, a vast area lying between Hawai'i, Rapa Nui, and New Zealand, is much debated and the underlying causes of this great migration have been enigmatic. Our study generates evidence for human dispersal into eastern Polynesia from islands to the west from around AD 900 and contemporaneous paleoclimate data from the likely source region. Lake cores from Atiu, Southern Cook Islands (SCIs) register evidence of pig and/or human occupation on a virgin landscape at this time, followed by changes in lake carbon around AD 1000 and significant anthropogenic disturbance from c. AD 1100. The broader paleoclimate context of these early voyages of exploration are derived from the Atiu lake core and complemented by additional lake cores from Samoa (directly west) and Vanuatu (southwest) and published hydroclimate proxies from the Society Islands (northeast) and Kiribati (north). Algal lipid and leaf wax biomarkers allow for comparisons of changing hydroclimate conditions across the region before, during, and after human arrival in the SCIs. The evidence indicates a prolonged drought in the likely western source region for these colonists, lasting c. 200 to 400 y, contemporaneous with the phasing of human dispersal into the Pacific. We propose that drying climate, coupled with documented social pressures and societal developments, instigated initial eastward exploration, resulting in SCI landfall(s) and return voyaging, with colonization a century or two later. This incremental settlement process likely involved the accumulation of critical maritime knowledge over several generations.


Subject(s)
Archaeology/methods , Droughts , Geologic Sediments/analysis , Human Migration/history , History, Ancient , Humans , Lakes , Polynesia
7.
Sci Total Environ ; 722: 137745, 2020 Jun 20.
Article in English | MEDLINE | ID: mdl-32199357

ABSTRACT

Many lakes undergo anthropogenically driven eutrophication and pollution leading to decreased water and sediment quality. These effects can enhance seasonally changing lake redox conditions that may concentrate potentially toxic elements. Here we report the results of a multi-method geochemical and sediment microfabric analysis applied to reconstruct the history of cultural eutrophication and pollution of the North and South Basins of Windermere, UK. Eutrophication developed from the mid-19th to the earliest 20th centuries. Enhanced lake productivity is indicated by increased sedimentary δ13C, and increased pollution by a higher concentration of metals (Pb, Hg, and As) in the sediment, likely enhanced by incorporation and adsorption to settling diatom aggregates, preserved as sedimentary laminae. In the South Basin, increasing sediment δ15N values occur in step with Zn, Hg, and Cu, linking metal enrichment to isotopically heavy nitrate (N) from anthropogenic sources. From around 1930, decreases in Mn and Fe-rich laminae indicate reduced deep-water ventilation, whereas periods of sediment anoxia increased, being most severe in the deeper North Basin. Strongly reducing sediment conditions promoted Fe and Mn reduction and Pb-bearing barite formation, hitherto only described from toxic mine wastes and contaminated soils. From 1980 there was an increase in indicators of bottom water oxygenation, although not to before 1930. But in the South Basin, the continued impacts of sewage are indicated by elevated sediment δ15N. Imaging and X-ray microanalysis using scanning electron microscopy has shown seasonal-scale redox mineralisation of Mn, Fe, and Ba related to intermittent sediment anoxia. Elevated concentrations of these metals and As also occur in the surficial sediment and provide evidence for dynamic redox mobilisation of potentially toxic elements to the lake water. Concentrations of As (up to 80 ppm), exceed international Sediment Quality Standards. This process may become more prevalent in the future with climate change driving lengthened summer stratification.

8.
Sci Rep ; 9(1): 6601, 2019 04 29.
Article in English | MEDLINE | ID: mdl-31036842

ABSTRACT

Conventional pollution monitoring strategies for heavy metals are often costly and unpractical. Innovative sampling and analytical approaches are therefore needed to efficiently monitor large areas. This study presents a novel, simple, fast, and inexpensive method to monitor heavy metal pollution that uses cation-exchange resin sachets and the micro-XRF core-scanning technique (XRF-CS). The resin passive samplers act as concentrators of cationic species and can be readily deployed spatially and temporally to record pollution signals. The large number of analytical tasks are then overcome by the fast and non-destructive XRF-CS to precisely assess elemental concentrations. Quantifying element loading involves direct comparison with a set of identically prepared and scanned resin reference standards containing Ca, Ti, Cr, Mn, Ni, Cu, Zn, Pb. The results show that within the test range (from 0-1000 s mg kg-1), the calibration lines have excellent regressions (R2 ≥ 0.97), even at the shortest exposure time (1 s). A pilot field survey of a suspected polluted area in central Taiwan, where 30 resin sachets had been deployed, identified a pollution hot spot in a rapid and economical manner. Therefore, this approach has the potential to become a valuable tool in environmental monitoring and forensics.

9.
Sci Total Environ ; 660: 1419-1432, 2019 Apr 10.
Article in English | MEDLINE | ID: mdl-30743935

ABSTRACT

Managed realignment (MR) schemes are being implemented to compensate for the loss of intertidal saltmarsh habitats by breaching flood defences and inundating the formerly defended coastal hinterland. However, studies have shown that MR sites have lower biodiversity than anticipated, which has been linked with anoxia and poor drainage resulting from compaction and the collapse of sediment pore space caused by the site's former terrestrial land use. Despite this proposed link between biodiversity and soil structure, the evolution of the sediment sub-surface following site inundation has rarely been examined, particularly over the early stages of the terrestrial to marine or estuarine transition. This paper presents a novel combination of broad- and intensive-scale analysis of the sub-surface evolution of the Medmerry Managed Realignment Site (West Sussex, UK) in the three years following site inundation. Repeated broad-scale sediment physiochemical datasets are analysed to assess the early changes in the sediment subsurface and the preservation of the former terrestrial surface, comparing four locations of different former land uses. Additionally, for two of these locations, high-intensity 3D-computed X-ray microtomography and Itrax micro-X-ray fluorescence spectrometry analyses are presented. Results provide new data on differences in sediment properties and structure related to the former land use, indicating that increased agricultural activity leads to increased compaction and reduced porosity. The presence of anoxic conditions, indicative of poor hydrological connectivity between the terrestrial and post-inundation intertidal sediment facies, was only detected at one site. This site has experienced the highest rate of accretion over the terrestrial surface (ca. 7 cm over 36 months), suggesting that poor drainage is caused by the interaction (or lack of) between sediment facies rather than the former land use. This has significant implications for the design of future MR sites in terms of preparing sites, their anticipated evolution, and the delivery of ecosystem services.

10.
Sci Rep ; 8(1): 9428, 2018 06 21.
Article in English | MEDLINE | ID: mdl-29930338

ABSTRACT

Microplastics are an increasingly important contaminant in the marine environment. Depending on their composition and degree of biofouling, many common microplastics are less dense than seawater and so tend to float at or near the ocean surface. As such, they may exhibit high concentrations in the sea surface microlayer (SML - the upper 1-1000 µm of the ocean) relative to deeper water. This paper examines the accumulation of microplastics, in particular microfibres, in the SML in two contrasting estuarine systems - the Hamble estuary and the Beaulieu estuary, southern U.K., via a novel and rapid SML-selective sampling method using a dipped glass plate. Microplastic concentrations (for identified fibres, of 0.05 to 4.5 mm length) were highest in the SML-selective samples (with a mean concentration of 43 ± 36 fibres/L), compared to <5 fibres/L for surface and sub-surface bulk water samples. Data collected show the usefulness of the dipped glass plate method as a rapid and inexpensive tool for sampling SML-associated microplastics in estuaries, and indicate that microplastics preferentially accumulate at the SML in estuarine conditions (providing a potential transfer mechanism for incorporation into upper intertidal sinks). Fibres are present (and readily sampled) in both developed and more pristine estuarine systems.

11.
Sci Total Environ ; 622-623: 325-336, 2018 May 01.
Article in English | MEDLINE | ID: mdl-29220760

ABSTRACT

The Gulf of Mexico is considered one of the world's major marine ecosystems, supporting important fisheries and habitats such as barrier islands, mangrove forests, seagrass beds, coral reefs etc. It also hosts a range of complex offshore petroleum exploration, extraction, and refining industries, which may have chronic or acute impacts on ecosystem functioning. Previous work on the marine effects of this activity is geographically incomplete, and has tended to focus on direct hydrocarbon impacts, while impacts from other related contaminants (e.g. heavy metals, salt-rich drilling muds) which may be discharged from oil facilities have not been widely assessed. Here, we examine historical trace element accumulation in marine sediments collected from four sites in the Tamaulipas shelf, Gulf of Mexico, in the area of the Arenque oil field. Dated sediment cores were used to examine the sources, and historical and contemporary inputs, of trace metals (including those typically present in oil industry discharges) and their potential biological impact in the Tamaulipas aquatic environment over the last 100years. CaO (i.e. biogenic component) normalized data showed increasing V, Cr, Zn, Cu, Pb, Zr and Ba towards the sediment surface in three of the four cores, with Ba and V (based on an adverse effect index) possibly associated with adverse effects on organisms. Dated Ba/CaO profiles show an increase of 30-137% after opening of oil installations in the study area, and can be broadly correlated with increasing oil industry activities across the wider Gulf of Mexico. Data do not record however a clear enhancement of Ba concentration in sediment cores collected near to oil platforms over more distal cores, indicating that any Ba released from drilling platforms is incorporated quickly into the sediments around the drilling sites, and once this element has been deposited its rate of resuspension and mobility is low. CAPSULE ABSTRACT: Sediment core data from the Tamaulipas shelf show the influence of oil industry activities on selected trace element concentrations, with Ba/CaO broadly correlating with increasing oil industry activities across the wider Gulf of Mexico.

12.
J Radioanal Nucl Chem ; 314(2): 651-658, 2017.
Article in English | MEDLINE | ID: mdl-29104338

ABSTRACT

Quantitative extraction of tritium from a sample matrix is critical to efficient measurement of the low-energy pure beta emitter. Oxidative pyrolysis using a tube furnace (Pyrolyser) has been adopted as an industry standard approach for the liberation of tritium (Warwick et al. in Anal Chim Acta 676:93-102, 2010) however pyrolysis of organic-rich materials can be problematic. Practically, the mass of organic rich sample combusted is typically limited to <1 g to minimise the possibility of incomplete combustion. This can have an impact on both the limit of detection that can be achieved and how representative the subsample is of the bulk material, particularly in the case of heterogeneous soft waste. Raddec International Ltd (Southampton, UK), in conjunction with GAU-Radioanalytical, has developed a new high-capacity oxygen combustion bomb (the Hyperbaric Oxidiser; HBO2) to address this challenge. The system is capable of quantitatively combusting samples of 20-30 g under an excess of oxygen, facilitating rapid extraction of total tritium from a wide range sample types.

13.
J Radioanal Nucl Chem ; 314(2): 753-760, 2017.
Article in English | MEDLINE | ID: mdl-29104339

ABSTRACT

Liquid scintillation spectrometry is widely used for the analysis of alpha and beta emitting radionuclides. Robust calibration of liquid scintillation (LS) spectrometers is fundamental to accurate LS measurement but at the same time is time consuming and costly, particularly if a wide range of radionuclides are analysed by the laboratory. The frequency of the calibration varies in different laboratories and is based on many practical and operational factors. This work summarizes the observations regarding variations in 1220 Quantulus spectrometers efficiency calibrations performed annually using various radionuclides: 3H 63Ni, 55Fe, 36Cl, 45Ca, 147Pm, 241Pu, 99Tc for a period of 9 years and discusses the implication to calibration frequency.

14.
J Radioanal Nucl Chem ; 314(2): 761-766, 2017.
Article in English | MEDLINE | ID: mdl-29104340

ABSTRACT

This paper describes an early-stage evaluation of a purpose-designed extraction/detection system that can be deployed by non-specialists either on-site or as part of a mobile laboratory. The system comprises three main components; (1) an optimised compact extraction system for recovery of radionuclides from the waste form; (2) an extraction test strip designed to recover the radionuclides from the waste digest; (3) a scintillation-based detection system capable of quantification of alpha, low energy beta and high energy beta emitting radionuclides. Data are presented on the preliminary assessment of the extraction/detection system for the measurement of 90Sr and 99Tc in aqueous wastes.

15.
Environ Sci Technol ; 51(17): 9488-9497, 2017 Sep 05.
Article in English | MEDLINE | ID: mdl-28768097

ABSTRACT

Estuarine sediments provide an important sink for contaminants discharged into fluvial, estuarine, and nearshore settings, and numerous authors have utilized this trapping function to assess historical contaminant loadings and contaminant breakdown/transformation processes. This Article examines the retention of elemental and isotopic sedimentary signatures in an industrialized estuarine system subject to a strongly upward sea-level trend, over a 20 year period. Two contrasting saltmarsh sites (at Hythe and Hamble, part of the wider Southampton Water estuarine system, UK) were examined, which had been previously cored and analyzed in the early 1990s. Much of the geochemical record of recent anthropogenic activity has been eroded and lost at the Hamble site. In contrast, radiometric, isotopic and elemental records of anthropogenic activity have been retained in the Hythe marsh, with 137Cs and Cu depth profiles showing retention of input maxima related to fallout and local industrial discharges, respectively. Stable Pb isotope data show a broad degree of correspondence in cores analyzed in 1994 and 2014 when plotted against sediment (radiometric) age, indicating the usefulness of isotopic data in retaining information on Pb sources and in disentangling Pb input histories. New ultrahigh precision, double-spike mass spectrometry stable Pb isotope data allow clearer discrimination of historical Pb input phases, and highlight within-estuary mixing and supply of reworked, secondary contamination from erosion of anthropogenically labeled sediments elsewhere in the estuary.


Subject(s)
Environmental Monitoring , Lead/analysis , Wetlands , Geologic Sediments , Isotopes , United Kingdom , Water Pollutants, Chemical
16.
Anal Chem ; 89(11): 6006-6014, 2017 06 06.
Article in English | MEDLINE | ID: mdl-28446019

ABSTRACT

There is an increasing demand for rapid and effective analytical tools to support nuclear forensic investigations of seized or suspect materials. Some methods are simply adapted from other scientific disciplines and can effectively be used to rapidly prepare complex materials for subsequent analysis. A novel sample fusion method is developed, tested, and validated to produce homogeneous, flux-free glass beads of geochemical reference materials (GRMs), uranium ores, and uranium ore concentrates (UOC) prior to the analysis of 14 rare earth elements (REE) via laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS). The novelty of the procedure is the production of glass beads using 9 parts high purity synthetic enstatite (MgSiO3) as the glass former with 1 part of sample (sample mass ∼1.5 mg). The beads are rapidly prepared (∼10 min overall time) by fusing the blended mixture on an iridium strip resistance heater in an argon-purged chamber. Many elements can be measured in the glass bead, but the rare earth group in particular is a valuable series in nuclear forensic studies and is well-determined using LA-ICP-MS. The REE data obtained from the GRMs, presented as chondrite normalized patterns, are in very good agreement with consensus patterns. The UOCs have comparable patterns to solution ICP-MS methods and published data. The attractions of the current development are its conservation of sample, speed of preparation, and suitability for microbeam analysis, all of which are favorable for nuclear forensics practitioners and geochemists requiring REE patterns from scarce or valuable samples.


Subject(s)
Forensic Sciences/methods , Laser Therapy , Mass Spectrometry/methods , Magnesium Silicates , Metals, Rare Earth , Reference Standards , Uranium
17.
New Phytol ; 213(2): 929-941, 2017 Jan.
Article in English | MEDLINE | ID: mdl-27678125

ABSTRACT

Sedimentary DNA (sedDNA) has recently emerged as a new proxy for reconstructing past vegetation, but its taphonomy, source area and representation biases need better assessment. We investigated how sedDNA in recent sediments of two small Scottish lakes reflects a major vegetation change, using well-documented 20th Century plantations of exotic conifers as an experimental system. We used next-generation sequencing to barcode sedDNA retrieved from subrecent lake sediments. For comparison, pollen was analysed from the same samples. The sedDNA record contains 73 taxa (mainly genus or species), all but one of which are present in the study area. Pollen and sedDNA shared 35% of taxa, which partly reflects a difference in source area. More aquatic taxa were recorded in sedDNA, whereas taxa assumed to be of regional rather than local origin were recorded only as pollen. The chronology of the sediments and planting records are well aligned, and sedDNA of exotic conifers appears in high quantities with the establishment of plantations around the lakes. SedDNA recorded other changes in local vegetation that accompanied afforestation. There were no signs of DNA leaching in the sediments or DNA originating from pollen.


Subject(s)
DNA, Plant/genetics , Geologic Sediments , Introduced Species , Lakes , Tracheophyta/genetics , Geography , Models, Theoretical , Pollen/genetics , Repetitive Sequences, Nucleic Acid/genetics , Scotland , Time Factors
18.
J Environ Radioact ; 162-163: 172-181, 2016 Oct.
Article in English | MEDLINE | ID: mdl-27267155

ABSTRACT

The application of Principal Components Analysis (PCA) to U and Th series gamma spectrometry data provides a discriminatory tool to help determine the provenance of illicitly recovered uranium ore concentrates (UOCs). The PCA is applied to a database of radiometric signatures from 19 historic UOCs from Australia, Canada, and the USA representing many uranium geological deposits. In this study a key process to obtain accurate radiometric data (gamma and alpha) is to digest the U-ores and UOCs using a lithium tetraborate fusion. Six UOCs from the same sample set were analysed 'blind' and compared against the database to identify their geolocation. These UOCs were all accurately linked to their correct geolocations which can aid the forensic laboratory in determining which further analytical techniques should be used to improve the confidence of the particular location.


Subject(s)
Environmental Monitoring/methods , Uranium/analysis , Principal Component Analysis , Spectrometry, Gamma
19.
Anal Chim Acta ; 900: 1-9, 2015 Nov 05.
Article in English | MEDLINE | ID: mdl-26572834

ABSTRACT

A rapid and effective preparative procedure has been evaluated for the accurate determination of low-energy (40-200 keV) gamma-emitting radionuclides ((210)Pb, (234)Th, (226)Ra, (235)U) in uranium ores and uranium ore concentrates (UOCs) using high-resolution gamma ray spectrometry. The measurement of low-energy gamma photons is complicated in heterogeneous samples containing high-density mineral phases and in such situations activity concentrations will be underestimated. This is because attenuation corrections, calculated based on sample mean density, do not properly correct where dense grains are dispersed within a less dense matrix (analogous to a nugget effect). The current method overcomes these problems using a lithium tetraborate fusion that readily dissolves all components including high-density, self-attenuating minerals/compounds. This is the ideal method for dissolving complex, non-volatile components in soils, rocks, mineral concentrates, and other materials where density reduction is required. Lithium borate fusion avoids the need for theoretical efficiency corrections or measurement of matrix matched calibration standards. The resulting homogeneous quenched glass produced can be quickly dissolved in nitric acid producing low-density solutions that can be counted by gamma spectrometry. The effectiveness of the technique is demonstrated using uranium-bearing Certified Reference Materials and provides accurate activity concentration determinations compared to the underestimated activity concentrations derived from direct measurements of a bulk sample. The procedure offers an effective solution for initial nuclear forensic studies where complex refractory minerals or matrices exist. It is also significantly faster, safer and simpler than alternative approaches.

20.
Anal Chim Acta ; 890: 7-20, 2015 Aug 26.
Article in English | MEDLINE | ID: mdl-26347165

ABSTRACT

Radionuclides of caesium are environmentally important since they are formed as significant high yield fission products ((135)Cs and (137)Cs) and activation products ((134)Cs and (136)Cs) during nuclear fission. They originate from a range of nuclear activities such as weapons testing, nuclear reprocessing and nuclear fuel cycle discharges and nuclear accidents. Whilst (137)Cs, (134)Cs and (136)Cs are routinely measurable at high sensitivity by gamma spectrometry, routine detection of long-lived (135)Cs by radiometric methods is challenging. This measurement is, however, important given its significance in long-term nuclear waste storage and disposal. Furthermore, the (135)Cs/(137)Cs ratio varies with reactor, weapon and fuel type, and accurate measurement of this ratio can therefore be used as a forensic tool in identifying the source(s) of nuclear contamination. The shorter-lived activation products (134)Cs and (136)Cs have a limited application but provide useful early information on fuel irradiation history and have importance in health physics. Detection of (135)Cs (and (137)Cs) is achievable by mass spectrometric techniques; most commonly inductively coupled plasma mass spectrometry (ICP-MS), as well as thermal ionisation (TIMS), accelerator (AMS) and resonance ionisation (RIMS) techniques. The critical issues affecting the accuracy and detection limits achievable by this technique are effective removal of barium to eliminate isobaric interferences arising from (135)Ba and (137)Ba, and elimination of peak tailing of stable (133)Cs on (135)Cs. Isobaric interferences can be removed by chemical separation, most commonly ion exchange chromatography, and/or instrumental separation using an ICP-MS equipped with a reaction cell. The removal of the peak tailing interference is dependent on the instrument used for final measurement. This review summarizes and compares the analytical procedures developed for determination of (135)Cs/(137)Cs, with particular focus on ICP-MS detection and the methods applied to interference separation.

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