Human settlement of East Polynesia earlier, incremental, and coincident with prolonged South Pacific drought.

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.

Development of a numerical simulation method for modelling column breakthrough from extraction chromatography resins.

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.

Fusion Bead Procedure for Nuclear Forensics Employing Synthetic Enstatite to Dissolve Uraniferous and Other Challenging Materials Prior to Laser Ablation Inductively Coupled Plasma Mass Spectrometry.

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.

Lake sedimentary DNA accurately records 20th Century introductions of exotic conifers in Scotland.

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.

The Fate of Contaminants and Stable Pb Isotopes in a Changing Estuarine Environment: 20 Years On.

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.

Calixarene-based extraction chromatographic separation of ¹³5Cs and ¹³7Cs in environmental and waste samples prior to sector field ICP-MS analysis.

Advances in the sensitivities achievable by sector field inductively coupled plasma mass spectrometry (ICP-SFMS) offer the prospect of low-level measurement of shorter and longer lived radionuclides, thus expanding options for environmental and radioactively contaminated land assessment. In ICP-SFMS, the critical requirement for accurate detection is the effective chemical separation of isobaric and polyatomic interferences prior to sample introduction. As instrumental detection limit capability improves, accurate radionuclide determination requires highly effective separation materials that combine high analyte selectivity with subsequent quantitative analyte recovery compatible with ICP-SFMS detection. Two radioactive isotopes measurable by ICP-SFMS are the high yield fission products (135)Cs and (137)Cs that have entered the environment as a result of anthropogenic nuclear activities. ICP-SFMS enables reliable measurement of (135)Cs/(137)Cs ratios, which can be used as a forensic tool in determining the source of nuclear contamination. The critical requirement for accurate detection is the effective removal of isobaric interferences from (135)Ba and (137)Ba prior to measurement. A number of exchange materials can effectively extract Cs; however, non-quantitative elution of Cs makes subsequent ICP-SFMS quantification challenging. A novel extraction chromatographic resin has been developed by dissolving calix[4]arene-bis(tert-octylbenzo-crown-6) (BOBCalixC6) in octan-1-ol and loading onto an Amberchrom CG-71 prefilter resin material. Preparation of the material takes less than 1 h and, at an optimal concentration of 3 M HNO3, shows high selectivity toward Cs, which is effectively eluted in 0.05 M HNO3. The procedure developed shows high Cs selectivity and Ba decontamination from digests of complex matrixes including a saltmarsh sediment contaminated by aqueous discharges from a nuclear fuel reprocessing facility. Repeated tests show the resin can be reused up to four times. For low-level ICP-SFMS quantification, more complex sample matrixes benefit from a cation resin cleanup stage prior to using BOBCalixC6 that serves to enhance Ba decontamination and Cs recovery.

Using thermal evolution profiles to infer tritium speciation in nuclear site metals: an aid to decommissioning.

Understanding the association and retention of tritium in metals has significance in nuclear decommissioning programs and can lead to cost benefits through waste reduction and recycling of materials. To develop insights, a range of metals from two nuclear sites and one non-nuclear site were investigated which had different exposure histories. Tritium speciation in metals was inferred through incremental heating experiments over the range of 20-900 °C using a Raddec Pyrolyser instrument. Systematic differences in thermal desorption profiles were found for nonirradiated and irradiated metals. In nonirradiated metals (e.g., stainless steel and copper), it was found that significant tritium had become incorporated following prolonged exposure to tritiated water vapor (HTO) or tritium/hydrogen gas (HT) in nuclear facilities. This externally derived tritium enters metals by diffusion with a rate controlled by the metal composition and whether the surface of the metal had been sealed or coated prior to exposure. The tritium is normally trapped in hydrated oxides lying along grain boundaries. In irradiated metals, an additional type of tritium can form internally through neutron capture reactions. The amount formed depends on the concentration and distribution of trace lithium and boron in the metal as well as the integrated neutron flux. Liberating this kind of tritium typically requires temperatures above 800 °C. The pattern of tritium evolution derived from simple thermal desorption experiments allows reliable inferences to be drawn on the likely origin, location, and phases that trap tritium. Any weakly bound tritium liberated at temperatures of ~100 °C is indicative of mostly HTO interactions in the metal. Any strongly bound tritium liberated over the range of 600-900 °C is indicative of neutrogenic tritium formed via neutron capture by trace Li and B. Neutron capture by lithium is likely to be more significant than for boron based on lithium's higher trace element abundance and neutron cross section. The time required for efficient thermal desorption of tritium ultimately depends on the metal composition, its tritium exposure history, integrated neutron flux, sample size, sample geometry, heating rate, and final desorption temperature.

Determination of precise ¹³5Cs/¹³7Cs ratio in environmental samples using sector field inductively coupled plasma mass spectrometry.

Recent advances in sector field inductively coupled plasma mass spectrometry (ICP-SFMS) have led to significant sensitivity enhancements that expand the range of radionuclides measurable by ICP-MS. The increasing capability and performance of modern ICP-MS now allows analysis of medium-lived radionuclides previously undertaken using radiometric methods. A new generation ICP-SFMS was configured to achieve sensitivities up to 80,000 counts per second for a 1 ng/L (133)Cs solution, providing a detection limit of 1 pg/L. To extend this approach to environmental samples it has been necessary to develop an effective chemical separation scheme using ultrapure reagents. A procedure incorporating digestion, chemical separation and quantification by ICP-SFMS is presented for detection of the significant fission product radionuclides of cesium ((135)Cs and (137)Cs) at concentrations found in environmental and low level nuclear waste samples. This in turn enables measurement of the (135)Cs/(137)Cs ratio, which varies with the source of nuclear contamination, and can therefore provide a powerful dating and forensic tool compared to radiometric detection of (137)Cs alone. A detection limit in sediment samples of 0.05 ng/kg has been achieved for (135)Cs and (137)Cs, corresponding to 2.0 × 10(-3) and 160 mBq/kg, respectively. The critical issue is ensuring removal of barium to eliminate isobaric interferences arising from (135)Ba and (137)Ba. The ability to reliably measure (135)Cs/(137)Cs using a high specification laboratory ICP-SFMS now enables characterization of waste materials destined for nuclear waste repositories as well as extending options in environmental geochemical and nuclear forensics studies.

A 500 year sediment lake record of anthropogenic and natural inputs to Windermere (English Lake District) using double-spike lead isotopes, radiochronology, and sediment microanalysis.

A high-resolution record of pollution is preserved in recent sediments from Windermere, the largest lake in the English Lake District. Data derived from X-ray core scanning (validated against wavelength dispersive X-ray fluorescence), radiochronological techniques ((210)Pb and (137)Cs) and ultrahigh precision, double-spike mass spectrometry for lead isotopes are combined to decipher the anthropogenic inputs to the lake. The sediment record suggests that while most element concentrations have been stable, there has been a significant increase in lead, zinc, and copper concentrations since the 1930s. Lead isotope down-core variations identify three major contributory sources of anthropogenic (industrial) lead, comprising gasoline lead, coal combustion lead (most likely source is coal-fired steam ships), and lead derived from Carboniferous Pb-Zn mineralization (mining activities). Periods of metal workings do not correlate with peaks in heavy metals due to the trapping efficiency of up-system lakes in the catchment. Heavy metal increases could be due to flood-induced metal inwash after the cessation of mining and the weathering of bedrock in the catchment. The combination of sediment analysis techniques used provides new insights into the pollutant depositional history of Windermere and could be similarly applied to other lake systems to determine the timing and scale of anthropogenic inputs.

Identification and quantification of radionuclides in contaminated drinking waters and pipeline deposits.

There is broad international interest, particularly with Homeland Security and first-responder organizations, in developing a range of effective, robust, and rapid analytical tools to identify terrorist assaults. Accidental or intentional radionuclide contamination of drinking water supplies would have significant public health, social, political, and financial implications even where the real risk might be small given public perception. Rapid identification and assessment of the magnitude of any contamination is critical in managing any threat and ultimately in allaying public and regulator concerns and in steering subsequent remediation operations. Conventional screening techniques do not provide information of the radionuclide present, and subsequent identification techniques are too time-consuming and require some prior knowledge of the nuclide identity to permit accurate quantification. The development described here presents a novel, rapid, and effective radiometric approach using industry-standard liquid scintillation counting equipment that can both identify and quantify alpha and beta radionuclide contamination within 1 h of sample receipt. The liquid scintillation counting (LSC) or liquid scintillation analysis (LSA) method, though widely used by the life science and the (14)C scientific communities since the 1960s, has greater potential than is often used. The technique developed here, which uses multiple quench parameters for nuclide identification, has been tested on both contaminated drinking waters and pipeline scales with compositions typical of those that might be encountered. It is shown to be highly effective both in terms of rapidly identifying the radionuclide and providing a measure of the quantity of radionuclide present. The whole procedure is about to be developed into an integrated analytical system for use by untrained personnel. It is notable that the development could also be readily applied as a QC procedure in routine radioanalytical measurements.

The distribution and enrichment of trace elements in surface and core sediments from the Changjiang River Estuary, China: Evidence for anthropogenic inputs and enhanced availability of rare earth elements (REE).

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.

Evidence for the preservation of technogenic tritiated organic compounds in an estuarine sedimentary environment.

The macrotidal Severn Estuary (southwestern UK) has received a broad range of industrial discharges since the beginning of the Industrial Revolution. A more recent anthropogenic input to the estuary has been technogenic tritium (specifically organically bound tritium, OBT). This was derived from a specialized industrial laboratory producing custom radiolabeled compounds for life science research and diagnostic testing from 1980 until 2008. While it was generally acknowledged that the radiological impact of the tritium discharges into the Estuary was small, public concern motivated the company and regulatory agencies to commission several research studies from 1998 to 2005 to better understand their environmental impact. This study examined OBT interaction with estuarine sediment by acquiring a broad range of geochemical and sedimentological data from a suite of sediment cores collected from the northern side of the Estuary. Two important observations are that the OBT compounds are strongly bound to the clay/silt fraction of sediment and that the down-core OBT profiles in intertidal and subtidal sediments are broadly similar to the discharge record. Geochemical and chronometric methods (Cu, Pb and Zn elemental profiles, (210)Pb, (137)Cs) provide important corroboration of the OBT record. A key additional piece of evidence that firmly authenticated the established chronology was the discovery of a previously unreported sedimentary marker layer that was generated by a major storm surge that occurred on December 13, 1981. Although this study has provided clear evidence of systematic accumulation of OBT in sedimentary sinks of the region, an estimation of its depositional inventory shows it represents only a small fraction of the total discharge. This modest retention in the principal sedimentary sinks of the Severn Estuary system reflects the particular dynamics of this highly macrotidal sediment starved estuary.

A compact, dual-zone vertical tube furnace for the determination of tritium and carbon-14 in decommissioning wastes.

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.

Environmental risk of trace metals and metalloids in estuarine sediments: An example from Southampton Water, U.K.

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.

Assessing the role of the "estuarine filter" for emerging contaminants: pharmaceuticals, perfluoroalkyl compounds and plasticisers in sediment cores from two contrasting systems in the southern U.K.

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.

Tracing lake pollution, eutrophication and partial recovery from the sediments of Windermere, UK, using geochemistry and sediment microfabrics.

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.

Sediment structure and physicochemical changes following tidal inundation at a large open coast managed realignment site.

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.

Rapid assessment of heavy metal pollution using ion-exchange resin sachets and micro-XRF core-scanning.

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.

Tritium speciation in nuclear reactor bioshield concrete and its impact on accurate analysis.

Tritium ((3)H) is produced in nuclear reactors via several neutron-induced reactions [(2)H(n, gamma)(3)H, (6)Li(n, alpha)(3)H, (10)B(n, 2alpha)(3)H, (14)N(n, (3)H)(12)C, and ternary fission (fission yield <0.01%)]. Typically, (3)H is present as tritiated water (HTO) and can become adsorbed into structural concrete from the surface inward where it will be held in a weakly bound form. However, a systematic analysis of a sequence of subsamples taken from a reactor bioshield using combustion and liquid scintillation analysis has identified two forms of (3)H, one weakly bound and one strongly bound. The strongly bound tritium, which originates from neutron capture on trace lithium ((6)Li) within mineral phases, requires temperatures in excess of 350 degrees C to achieve quantitative recovery. The weakly bound form of tritium can be liberated at significantly lower temperatures (100 degrees C) as HTO and is associated with dehydration of hydrous mineral components. Without an appreciation that two forms of tritium can exist in reactor bioshields, the (3)H content of samples may be severely underestimated using conventional analytical approaches. These findings exemplify the need to develop robust radioactive waste characterization procedures in support of nuclear decommissioning programs.

Historical trace element accumulation in marine sediments from the Tamaulipas shelf, Gulf of Mexico: An assessment of natural vs anthropogenic inputs.

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.