Revisiting five decades of Th-234 data: a comprehensive global oceanic compilation

© The Author(s), 2022. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Ceballos-Romero, E., Buesseler, K. O., & Villa-Alfageme, M. Revisiting five decades of Th-234 data: a comprehensive global oceanic compilation. Earth System Science Data, 14(6), (2022): 2639–2679, https://doi.org/10.5194/essd-14-2639-2022.We present here a global oceanic compilation of 234Th measurements that collects results from researchers and laboratories over a period exceeding 50 years. The origin of the 234Th sampling in the ocean goes back to 1967, when Bhat et al. (1969) initially studied 234Th distribution relative to its parent 238U in the Indian Ocean. However, it was the seminal work of Buesseler et al. (1992) – which proposed an empirical method to estimate export fluxes from 234Th distributions – that drove the extensive use of the 234Th–238U radioactive pair to evaluate the organic carbon export out of the surface ocean by means of the biological carbon pump. Since then, a large number of 234Th depth profiles have been collected using a variety of sampling instruments and strategies that have changed during the past 50 years. The present compilation is made of a total 223 data sets: 214 from studies published in either articles in refereed journals, PhD theses, or repositories, as well as 9 unpublished data sets. The data were compiled from over 5000 locations spanning all the oceans for total 234Th profiles, dissolved and particulate 234Th activity concentrations (in dpm L−1), and POC:234Th ratios (in µmol dpm−1) from both sediment traps and filtration methods. A total of 379 oceanographic expeditions and more than 56 600 234Th data points have been gathered in a single open-access, long-term, and dynamic repository. This paper introduces the dataset along with informative and descriptive graphics. Appropriate metadata have been compiled, including geographic location, date, and sample depth, among others. When available, we also include water temperature, salinity, 238U data (over 18 200 data points), and particulate organic nitrogen data. Data source and method information (including 238U and 234Th) is also detailed along with valuable information for future data analysis such as bloom stage and steady-/non-steady-state conditions at the sampling moment. The data are archived on the PANGAEA repository, with the dataset DOI https://doi.org/10.1594/PANGAEA.918125 (Ceballos-Romero et al., 2021). This provides a valuable resource to better understand and quantify how the contemporary oceanic carbon uptake functions and how it will change in future.This work was partially funded by the V Research Programme from the Universidad de Sevilla (Elena Ceballos-Romero) and EU FEDER-Junta de Andalucía funded project US-1263369 (María Villa-Alfageme). Ken O. Buesseler was supported in part by NSF under GEOTRACES, NASA as part of the EXPORTS program, and WHOI as part of the Ocean Twilight Zone project. María Villa-Alfageme and Ken O. Buesseler are also part of an IAEA Coordinated Research Project “Behaviour and effects of natural and anthropogenic radionuclides in the marine environment and their use as tracers for oceanographic studies

The behaviour of 236-U in the North Atlantic Ocean assessed from numerical modelling: A new evaluation of the input function into the Arctic

-A numerical model, previously validated with other radionuclides, was applied to simulate the dispersion of 236U released from European nuclear fuel reprocessing plants in the North Atlantic and Shelf Seas using a published reconstruction of Sellafield and La Hague releases. Model results are in better agreement with observations if the lowest estimation of such releases are used. This implies that approximately 40 kg of 236U has been discharged from Sellafield. It was found that adsorption of 236U on bed sediments of the shallow European Shelf Seas plays an essential role in its dispersion patterns. This contrasts strongly with the more conservative behaviour of 129I in the same area. This has two important implications in the use of 236U as oceanographic tracer; i) special care must be taken in coastal areas, as sediments might act as sinks and sources of 236U; ii) the annual input function of 236U into the Arctic is not directly controlled by the annual discharges from Sellafield and La Hague, since sediments from the Irish, Celtic and North Sea modulate and smooth the signal. Only 52% of the total releases enter into the Arctic Ocean

The GEOTRACES Intermediate Data Product 2017

The GEOTRACES Intermediate Data Product 2017 (IDP2017) is the second publicly available data product of the international GEOTRACES programme, and contains data measured and quality controlled before the end of 2016. The IDP2017 includes data from the Atlantic, Pacific, Arctic, Southern and Indian oceans, with about twice the data volume of the previous IDP2014. For the first time, the IDP2017 contains data for a large suite of biogeochemical parameters as well as aerosol and rain data characterising atmospheric trace element and isotope (TEI) sources. The TEI data in the IDP2017 are quality controlled by careful assessment of intercalibration results and multi-laboratory data comparisons at crossover stations. The IDP2017 consists of two parts: (1) a compilation of digital data for more than 450 TEIs as well as standard hydrographic parameters, and (2) the eGEOTRACES Electronic Atlas providing an on-line atlas that includes more than 590 section plots and 130 animated 3D scenes. The digital data are provided in several formats, including ASCII, Excel spreadsheet, netCDF, and Ocean Data View collection. Users can download the full data packages or make their own custom selections with a new on-line data extraction service. In addition to the actual data values, the IDP2017 also contains data quality flags and 1-σ data error values where available. Quality flags and error values are useful for data filtering and for statistical analysis. Metadata about data originators, analytical methods and original publications related to the data are linked in an easily accessible way. The eGEOTRACES Electronic Atlas is the visual representation of the IDP2017 as section plots and rotating 3D scenes. The basin-wide 3D scenes combine data from many cruises and provide quick overviews of large-scale tracer distributions. These 3D scenes provide geographical and bathymetric context that is crucial for the interpretation and assessment of tracer plumes near ocean margins or along ridges. The IDP2017 is the result of a truly international effort involving 326 researchers from 25 countries. This publication provides the critical reference for unpublished data, as well as for studies that make use of a large cross-section of data from the IDP2017. This article is part of a special issue entitled: Conway GEOTRACES - edited by Tim M. Conway, Tristan Horner, Yves Plancherel, and Aridane G. González

Self-cleaning in an estuarine area formerly affected by 226Ra anthropogenic enhancements: numerical simulations

A numerical model of the Odiel–Tinto estuary (Spain) has been developed to study the self-cleaning process that was evidenced from 226Ra measurements in water and sediments collected in the period 1999–2002, after direct releases from a fertilizer complex ceased (in 1998). The hydrodynamic model is first calibrated, and standard tidal analysis is carried out to calculate tidal constants required by the dispersion code to determine instantaneous water currents and elevations over the estuary. In this way, long-term simulations may be carried out. The dispersion code includes advective/diffusive transport of radionuclides plus exchanges with bottom sediments described through a kinetic approach. The dispersion model is first tested by comparing computed and measured 226Ra concentrations over the estuary resulting after releases in the Odiel and Tinto rivers. Next, it is applied to simulate the self-cleaning process of the estuary. The time evolution of radium concentrations in bed sediments is in generally good agreement with observations. The computed sediment halving time of the estuary is 510 days, which also is in good agreement with that estimated from measurement

Self-cleaning in an estuarine area formerly affected by 226Ra anthropogenic enhancements

The estuary of the Odiel River has been affected by both direct discharges of phosphogypsum (radium enriched industrial waste) and dissolution and weathering of the exposed piles where this radium enriched waste was stored. In 1998 the waste management policy for industries changed. The direct discharges stopped and the new phosphogypsum piles were well protected against dissolution processes, avoiding any transference of radium into the environment. This work presents a study of the evolution with time (1999–2002) of the levels of 226Ra in river water and sediment samples with the new waste management policy. A liquid scintillation technique was used to measure the 226Ra activity concentration in sediment samples. A gas-proportional counter was also used to measure the 226Ra activity concentration in river water samples. The main conclusion is that a systematic and continuous decrease of the activity concentration of 226Ra with time in the Odiel River estuary is occurring. Thus, a possible self-cleaning in the estuary, once the direct waste discharges were avoided, can be inferred

234Th-derived particle fluxes and seasonal variability: when is the ss assumption reliable? Insights from a novel Approach for carbon flux simulation

Th measurements are widely used to estimate the downward carbon flux of particles via the oceanic Biological Pump. Carbon export is evaluated from 234Th-238U disequilibrium assuming either steady state (SS) conditions, or including a non-SS (NSS) correction. We use a novel stochastic simulation to quantify the temporal variation of vertical carbon and 234Th (dissolved and particulate) concentration profiles with high temporal resolution. We calculate seasonal export as if in situ measured with sediment trap and SS- and NSS-234ThapproachesandquantifytheperiodsofvalidityforSS/NSSconditionsdefinedinpreviousworks.The SS approach is valid throughout the entire season in oligotrophic regions. In temperate regions, the SS introduces a bias in the export if sampling takes place outside specific temporal windows. Windows of validity range from days in short blooms of ~15-day duration to weeks in blooms longer than ~30 days

The behaviour of I-129 released from nuclear fuel reprocessing factories in the North Atlantic Ocean and transport to the Arctic assessed from numerical modelling

A quantitative evaluation of the fate of 129I, released from the European reprocessing plants of Sellafield (UK) and La Hague (France), has been made by means of a Lagrangian dispersion model. Transport of radionuclides to the Arctic Ocean has been determined. Thus, 5.1 and 16.6 TBq of 129I have been intro-duced in the Arctic from Sellafield and La Hague respectively from 1966 to 2012. These figures represent, respectively, 48% and 55% of the cumulative discharge to that time. Inventories in the North Atlantic, including shelf seas, are 4.4 and 13.8 TBq coming from Sellafield and La Hague respectively. These figures are significantly different from previous estimations based on field data. The distribution of these inven-tories among several shelf seas and regions has been evaluated as well. Mean ages of tracers have been finally obtained, making use of the age-averaging hypothesis. It has been found that mean ages for Sellafield releases are about 3.5 year larger than for La Hague releases.European Union FP7 EURATOM project PREPARE 323287Ministerio de Ciencia, Innovación y Universidades FIS2012–3185

Recycling Bio-BasedWastes into Road-Base Binder: Mechanical, Leaching, and Radiological Implications

This work presents a physical, mechanical, durability, leaching, and radiological assay of three wastes (egg and scallop shells and olive pomace ash) as road-base binders. Two different waste/Portland-cement ratios (7.5/92.5 and 80/20) were studied. Density and compressive strength decreased when different wastes were added in every proportion. Additions of 7.5% of both shells reduce the density to about 2.5% and the compressive strength to 20%, while 80% reduces the density to 20% and the compressive strength to 90%, while the addition of biomass fly ash decreases the density and compressive strength in a higher proportion than shells. The durability against acid attack is increased when the three wastes are used, and this increase is higher when the waste dosage is increased (up to 15 times more when 80% biomass ash is used). With respect to leaching, scallop and eggshells can be used as a component of hydraulic road binder, but olive pomace ash presents leaching values higher than the limits of different regulations (Se, Pb, Ni, Mo, Cu, and As). From a radiological perspective, all road-base binders present an activity concentration index lower than 1, except when olive pomace ash was used, and the binders showed higher values of 40K due to the high potassium content of fly ash

Uranium immobilization by FEBEX bentonite and steel barriers in hydrothermal conditions

FEBEX clay is considered a reference material in engineered barriers for safe storage of nuclear waste and uranium is a minor component of high-level radioactive waste (HLRW) and a main component of the spent nuclear fuel (SNF). Here, the kinetics of reaction of uranium with FEBEX was investigated in addition to the uranium immobilisation ability and the structural analysis of the reaction products. Hydrothermal treatments were accomplished with UO22+ and tetravalent actinide simulator ZrO2+, also present in HLRW. The quantification of the reaction was performed through gamma spectrometry of uranium. Two mechanisms for UO22+ retention by FEBEX were detected: adsorption and formation of stable and insoluble new phases. The structural analyses performed using ZrO2+, confirmed the uranium adsorption and the presence of new phases, ZrO2 and Zr(SiO4), that emphasise the existence of a chemical reaction with the bentonite. The analysis of the velocity of reaction uranium-clay minerals revealed temperature dependence. An exponential fitting suggested that the removal of uranium from solution at temperatures over 200 °C could be completed in less than a year. For lower temperatures, several years are needed. Milliequivalents of UO22+ immobilised by the clay depended on temperature and time and were over cation exchange capacity (CEC) of FEBEX even at 100 °C (reaching 600% of CEC). The reaction with steel, also temperature dependent, was finally analysed. At 200 °C 40–70% of uranium reacted with steel. But only 30–15% reacted at 300 °C and 100 °C. The reactions provide a stable immobilisation mechanism for uranium even when its sorption and swelling capacities fail. Our experiments will be of particular interest for very deep borehole disposals were higher temperatures and pressures are expected.ENRESA 0079000121FEDER Junta de Andalucía P12-FQM-56

Contamination and restoration of an estuary affected by phosphogypsum releases

The Huelva Estuary in Huelva, Spain, has been one of the most studied environmental compartments in the past years from the point of view of naturally occurring radioactive material (NORM) releases. It has been historically affected by waste releases, enriched in radionuclides from the U-decay series, from factories located in the area devoted to the production of phosphoric acid and phosphate fertilizers. Nevertheless, changes in national regulations forced a new waste management practice in 1998, prohibiting releases of phosphogypsum into the rivers. The input of natural radionuclides from phosphate factories to rivers was drastically reduced. Because of this there was a unique opportunity for the study of the response of a contaminated environmental compartment, specifically an estuary affected by tidal influences, after the cessation of the contaminant releases to, in this case, the Huelva Estuary (henceforth referred to as the Estuary). To investigate the environmental response to this new discharge regime, the specific activities of radionuclides 226Ra and 210Pb in water and sediment samples collected in four campaigns (from 1999 to 2005) were determined and compared with pre-1998 values. From this study it is possible to infer the most effective mechanisms of decontamination for the Estuary. Decontamination rates of 210Pb and 226Ra in the sediments and water have been calculated using exponential fittings and corresponding half-lives have been deduced from them. The cleaning half-life in the whole area of the Estuary is about 6 and 3.5 years for 226Ra and 210Pb respectively. The observed trend clearly shows that contamination of the Estuary by natural radionuclides is now decreasing and radioactive levels in waters and sediments are approaching the natural background references. This work attempts to evaluate whether it can be expected that the decontamination of the enhanced levels of natural radioactivity in the Estuary can be performed via natural processe