Using radium isotopes to characterize water ages and coastal mixing rates: A sensitivity analysis

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W., 2006, PAPERS SUMMER UNDERG, P51 Taniguchi M, 2003, BIOGEOCHEMISTRY, V66, P35, DOI 10.1023/B:BIOG.0000006090.25949.8d Taylor J. R., 1997, INTRO ERROR ANAL, P160 Turner IL, 1997, J COASTAL RES, V13, P46 Weinstein Y., 2006, RADIOACT ENV, V8, P360, DOI DOI 10.1016/S1569-4860(05)08029-0 Windom HL, 2006, MAR CHEM, V102, P252, DOI 10.1016/j.marchem.2006.06.016 Knee, Karen L. Garcia-Solsona, Ester Garcia-Orellana, Jordi Boehm, Alexandria B. Paytan, Adina 4 AMER SOC LIMNOLOGY OCEANOGRAPHY WACO LIMNOL OCEANOGR-METHNumerous studies have used naturally occurring Ra isotopes (Ra-223, Ra-224, Ra-226, and Ra-228, with half-lives of 11.4 d, 3.7 d, 1600 y, and 5.8 y, respectively) to quantify water mass ages, coastal ocean mixing rates, and submarine groundwater discharge (SGD). Using Monte Carlo models, this study investigated how uncertainties in Ra isotope activities and the derived activity ratios (AR) arising from analytical uncertainty and natural variability affect the uncertainty associated with Ra-derived water ages and eddy diffusion coefficients, both of which can be used to calculate SGD. Analytical uncertainties associated with Ra-224, Ra-226, and Ra-228 activities were reported in most published studies to be less than 10% of sample activity; those reported for Ra-223 ranged from 7% to 40%. Relative uncertainty related to natural variability-estimated from the variability in Ra-223 and Ra-224 activities of replicate field samples-ranged from 15% to 50% and was similar for Ra-223 activity, Ra-224 activity, and the Ra-224/Ra-223 AR. Our analysis revealed that AR-based water ages shorter than 3-5 d often have relative uncertainties greater than 100%, potentially limiting their utility. Uncertainties in eddy diffusion coefficients estimated based on cross-shore gradients in short-lived Ra isotope activity were greater when fewer points were used to determine the linear trend, when the coefficient of determination (R-2) was low, and when Ra-224, rather than Ra-223, was used. By exploring the uncertainties associated with Ra-derived water ages and eddy diffusion coefficients, this study will enable researchers to apply these methods more effectively and to reduce uncertainty

Groundwater and nutrient discharge through karstic coastal springs (Castelló, Spain)

Altres ajuts: Support from the Fulbright Commission for a post-doctoral fellowship to J.G-O. (ref 2007-0516) is gratefully acknowledged. Support for the research of PM was received through the prize ICREA Academia, funded by the Generalitat de Catalunya.Discharge of groundwater and associated chemical compounds into coastal karstic regions, which are abundant in the Mediterranean basin, is envisaged to be significant. In this study, we evaluate the groundwater discharge and its nutrient load to the open karstic site of Badum (Castelló, East Spain). Salinity profiles evidenced that groundwater discharge from coastal brackish springs causes a buoyant fresher layer, as identified with thermal infrared images. Chemical tracers (radium isotopes, dissolved inorganic silicate and seawater major elements) have been used to determine a brackish groundwater proportion in coastal waters of 36% in October 2006 and 44% in June 2007. Based on a radium-derived residence time of 2.7 days in October 2006 and 2.0 days in June 2007, total SGD fluxes have been estimated in 71 500 and 187 000m³ d⁻¹, respectively, with fresh-SGD contributions representing 71% and 85%. The calculated SGD-associated nutrient fluxes, most likely of natural origin, were 1500 and 8300 μmolm⁻² d⁻¹ of DIN and 19 and 40 μmolm⁻² d⁻¹ of DIP in October 2006 and June 2007, respectively. These inputs may actually lead to or enhance P limitation, thereby altering the structure of biological communities in the area

Evaluation of 224Ra as a tracer for submarine groundwater discharge in Long Island Sound (NY)

Altres ajuts: the government of Spain and the Fulbright Commission for a post-doctoral fellowship to J.G-O. (ref 2007-0516)The approach to quantify submarine groundwater discharge using Ra isotopes generally involves developing a Ra mass balance in an estuary, bay or lagoon. In this work we present a 224Ra mass balance used to evaluate the importance of the submarine groundwater discharge (SGD) in Long Island Sound (NY, US), the third most important estuary in US, located between Long Island and Connecticut that is usually affected by summertime hypoxia in the western basin. Three surveys were conducted between April 2009 and August 2010 where 25 water stations were sampled for Ra isotopes, oxygen and Mn. Stations were oriented along 4 transects: one axial extending from the western to the eastern Sound and three longitudinal transects in the western, central and eastern Sound. The inventory of 224Ra in the water column in summer was circa 2 times greater than in winter, suggesting an increased 224Ra flux to the Sound in summer. A mass balance for 224Ra was constructed considering tidal exchange, inputs from rivers, desorption from resuspended particles, diffusive fluxes (including bioirrigation) from bottom sediments and radioactive decay in the water column. Fluxes of 224Ra from bottom sediments were measured by incubating cores under oxic conditions in a continuous flow mode such that the overlying water was circulated through a Mn-oxide fiber to maintain a constant activity of 224Ra. Fluxes from muddy sediments (comprising ~67% of the Sound bottom) ranged from 127 to 312dpmm-2d-1 and were ~60dpmm-2d-1 in sandy sediments (33% of the Sound). Incubations under hypoxic conditions showed variable fluxes depending on reduction and mobilization of Mn. The 224Ra mass balance shows a net input of Ra to the Sound of 106±50×1012dpmy-1 in spring and 244±112×1012dpmy-1 in the summer that is attributed to SGD. Elevated 224Ra values were observed near shore and in the pore fluids of the coarse beach sands along the Long Island and Connecticut coasts, suggesting that SGD driven by tidal recirculation through the beach face is a major source of 224Ra to the Sound. Seasonal variation in this source seems unlikely, and the calculated 224Ra SGD fluxes for spring and summer overlap within the uncertainties. Nevertheless we conclude that variations in the 224Ra water column inventories could be produced by seasonal changes in bioirrigation and/or redox cycling of Mn as well as sediment resuspension and desorption of 224Ra from resuspended particles, and that our mass balance underestimates these terms, particularly in the summer. 224Ra fluxes from sediments in estuaries, especially those with significant areas of muddy sediments and seasonal hypoxia, are important and should be well constrained in future uses of this isotope as a tracer for SGD

Tracing U mobility in deep groundwater using Ra isotopes

The mobility of natural U is compared among four boreholes in a fractured granite using Ra isotopes and geochemical modelling. Rn-222/Ra-226 activity ratios (ARs) spanning an order of magnitude underline differences in reactive surface area. (Ra-224/Ra-228)(ARs) up to 9 indicate recent changes in hydrogeochemistry, and (Ra-226/Ra-228)(ARs) 0.6-30 indicate variable deposition of U. Dissolved U is related to dissolution of a solid U(VI) phase by groundwater with HCO3- > 20 mg.L-1. U reduction is hindered by Ca2UO2(CO3)(3)(0)

Datació absoluta de ceràmica pretalaiòtica de l'illa de Menorca

La datació mitjançant termoluminiscència de ceràmiques prehistòriques de la naveta d'enterrament de tipus intermedi de Biniac-l'Argentina de l'illa de Menorca, proporciona edats que perrneten documentar el grup cultural pretalaiotic en dates que van del segle XXIV al XVI a.e. Aquests resultats complementen l'esquema cronològic de la prehistòria de Menorca en un període del qual no es disposava de cap tipus de dates absolutes. Les dates aportades perrneten suposar per a la naveta una major antiguitat de l'acceptada generalment. Així doncs, caldrà esperar noves dates absolutes que confirmin aquesta tendència a situar a grans trets el complex cultural pretalaiòtic en un moment que compren el III mil·leni i la primera meitat del II a.C. ria de Menorca, cultura pretalaiotica, datació absoluta, terrnoluminiscencia, ceramica.Therrnoluminescence dating of prehistoric pottery from the intermediate type burial naveta in Biniac-l' Argentina (Minorca island), provides ages that perrnit to place the retalaiothic cultural group between the XXIV and XVII centuries b.e. These results fill sorne gaps in the chronological scheme of Minorca prehistory during a period in which no absolute dates were available. The dates indicate that the naveta is older than generally accepted. Therefore, to confirrn that the pretalaiothic cultural complex existed in a period comprised between the III rnillennium and the first half of the II b.C, we should wait for new absolute dates

Radium mass balance sensitivity analysis for submarine groundwater discharge estimation in semi-enclosed basins: the case study of Long Island Sound

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Tamborski, J., Cochran, J. K., Bokuniewicz, H., Heilbrun, C., Garcia-Orellana, J., Rodellas, V., & Wilson, R. Radium mass balance sensitivity analysis for submarine groundwater discharge estimation in semi-enclosed basins: the case study of Long Island Sound. Frontiers in Environmental Science, 8, (2020): 108, doi:10.3389/fenvs.2020.00108.Estimation of submarine groundwater discharge (SGD) to semi-enclosed basins by Ra isotope mass balance is herein assessed. We evaluate 224Ra, 226Ra, and 228Ra distributions in surface and bottom waters of Long Island Sound (CT-NY, United States) collected during spring 2009 and summer 2010. Surface water and bottom water Ra activities display an apparent seasonality, with greater activities during the summer. Long-lived Ra isotope mass balances are highly sensitive to boundary fluxes (water flux and Ra activity). Variation (50%) in the 224Ra, 226Ra, and 228Ra offshore seawater activity results in a 63–74% change in the basin-wide 226Ra SGD flux and a 58–60% change in the 228Ra SGD flux, but only a 4–9% change in the 224Ra SGD flux. This highlights the need to accurately constrain long-lived Ra activities in the inflowing and outflowing water, as well as water fluxes across boundaries. Short-lived Ra isotope mass balances are sensitive to internal Ra fluxes, including desorption from resuspended particles and inputs from sediment diffusion and bioturbation. A 50% increase in the sediment diffusive flux of 224Ra, 226Ra, and 228Ra results in a ∼30% decrease in the 224Ra SGD flux, but only a ∼6–10% decrease in the 226Ra and 228Ra SGD flux. When boundary mixing is uncertain, 224Ra is the preferred tracer of SGD if sediment contributions are adequately constrained. When boundary mixing is well-constrained, 226Ra and 228Ra are the preferred tracers of SGD, as sediment contributions become less important. A three-dimensional numerical model is used to constrain boundary mixing in Long Island Sound (LIS), with mean SGD fluxes of 1.2 ± 0.9 × 1013 L y–1 during spring 2009 and 3.3 ± 0.7 × 1013 L y–1 during summer 2010. The SGD flux to LIS during summer 2010 was one order of magnitude greater than the freshwater inflow from the Connecticut River. The maximum marine SGD-driven N flux is 14 ± 11 × 108 mol N y–1 and rivals the N load of the Connecticut River.This project has been funded by New York Sea Grant projects (R/CCP-16 and R/CMC-12). This research is contributing to the ICTA-UAB Unit of Excellence “María de Maeztu” (MDM-2015-0552) and MERS (2017 SGR – 1588, Generalitat de Catalunya). VR acknowledges financial support from the Beatriu de Pinós postdoctoral program of the Catalan Government (2017-BP-00334)

Intertidal percolation through beach sands as a source of 224,223 Ra to Long Island Sound, New York, and Connecticut, United States

Along tidal coasts, seawater circulated through the intertidal beach contributes to submarine groundwater discharge (SGD) and its associated geochemical signature. The short-lived radium isotopes, 223Ra (half-life = 11.4 d) and 224Ra (half-life = 3.66 d), were used to quantify this component of SGD in a large estuary, Long Island Sound (LIS), New York, United States. The tide is semidiurnal with a range of approximately 2 m. Concentrations in beach pore waters ranged from 97 to 678 disintegrations per minute (dpm) 224Ra 100 L–1, whereas concentrations in open coastal waters ranged from approximately 12 to 69 dpm 224Ra 100 L–1. A simple model based on ingrowth of 224Ra in the pore water of the beach sands was used to determine residence times of 0.6 to 2.5 d for water in the intertidal beach. Both 223Ra and 224Ra showed decreasing gradients and concentration in an offshore transect away from the beach face in Smithtown Bay, whereas the long-lived radium isotopes, 228Ra (half-life = 5.75 y) and 226Ra (half-life = 1,600 y), showed no significant gradients. Based on the 224Ra gradient, the flux across the LIS shoreline was estimated to be 1.79 × 108 dpm m–1 y–1. The 224Ra inventories in two zones, 0–50 m and 0–100 m offshore, were used to estimate total SGD fluxes of 3.1 × 1010 to 6.6 × 1010 m3 y–1 of intertidal seawater to the nearshore of LIS. Comparison of this estimate with hydrodynamic models of fresh groundwater flow in the adjacent coastal aquifer suggests that less than 1% of the SGD is freshwater

Separation and measurement of Pa, Th, and U isotopes in Marine sediments by microwave-assisted digestion and multiple collector inductively coupled plasma mass spectrometry

This manuscript describes a new protocol for determination of Pa/Th/U in marine sediments. It is based on microwave-assisted digestion and represents an important reduction of working time over conventional hot-plate digestion methods, and the use of HClO(4) is avoided. Although Th and U are completely dissolved with a first microwave step, around 40% of (231)Pa remains undissolved, and a short hot-plate step with reverse aqua regia is required to achieve total digestion and spike equilibration. Next, the method involves a separation of these elements and a further purification of the Pa fraction using Dowex AG1-X8 resin. Separation with Bio-Rad and Sigma-Aldrich resins was compared; although both perform similarly for Th and U, Pa yields are higher with Bio-Rad. Finally, samples are measured using a Nu instruments multiple collector inductively coupled plasma mass spectrometer (MC-ICPMS). Overall chemical yields range around 50% for Pa, 60% for Th, and 70% for U

Reviews and syntheses: 210Pb-derived sediment and carbon accumulation rates in vegetated coastal ecosystems-setting the record straight

Vegetated coastal ecosystems, including tidal marshes, mangroves and seagrass meadows, are being increasingly assessed in terms of their potential for carbon dioxide sequestration worldwide. However, there is a paucity of studies that have effectively estimated the accumulation rates of sediment organic carbon (Corg), also termed blue carbon, beyond the mere quantification of Corg stocks. Here, we discuss the use of the 210Pb dating technique to determine the rate of Corg accumulation in these habitats. We review the most widely used 210Pb dating models to assess their limitations in these ecosystems, often composed of heterogeneous sediments with varying inputs of organic material, that are disturbed by natural and anthropogenic processes resulting in sediment mixing and changes in sedimentation rates or erosion. Through a range of simulations, we consider the most relevant processes that impact the 210Pb records in vegetated coastal ecosystems and evaluate how anomalies in 210Pb specific activity profiles affect sediment and Corg accumulation rates. Our results show that the discrepancy in sediment and derived Corg accumulation rates between anomalous and ideal 210Pb profiles is within 20% if the process causing such anomalies is well understood. While these discrepancies might be acceptable for the determination of mean sediment and Corg accumulation rates over the last century, they may not always provide a reliable geochronology or historical reconstruction. Reliable estimates of Corg accumulation rates might be difficult at sites with slow sedimentation, intense mixing and/or that are affected by multiple sedimentary processes. Additional tracers or geochemical, ecological or historical data need to be used to validate the 210Pbderived results. The framework provided in this study can be instrumental in reducing the uncertainties associated with estimates of Corg accumulation rates in vegetated coastal sediments.This work was funded by the CSIRO Flagship Marine & Coastal Carbon Biogeochemical Cluster (Coastal Carbon Cluster), the Spanish Ministry of Economy and Competitiveness (projects EstresX CTM2012-32603, MedShift CGL2015-71809-P), the Generalitat de Catalunya (MERS 2017 SGR – 1588), the Australian Research Council LIEF Project (LE170100219), the Edith Cowan University Faculty Research Grant Scheme and the King Abdullah University of Science and Technology (KAUST) through baseline funding to Carlos M. Duarte. This work contributes to the ICTA Unit of Excellence (MinECo, MDM2015-0552