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  • 1
    Publication Date: 2022-10-26
    Description: © 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., Brown, C., Bokuniewicz, H., Cochran, J. K., & Rasbury, E. T. Investigating boron isotopes for identifying nitrogen sources supplied by submarine groundwater discharge to coastal waters. Frontiers in Environmental Science, 8, (2020): 126, doi:10.3389/fenvs.2020.00126.
    Description: Stable isotopes of oxygen, nitrogen, and boron were used to identify the sources of nitrate (NO3–) in submarine groundwater discharge (SGD) into a large tidal estuary (Long Island Sound, NY, United States). Potential contaminants such as manure, septic waste and fertilizer overlap in δ15N and δ18O but have been shown to have distinctive δ11B in non-coastal settings. Two distinct subterranean estuaries were studied with different land-use up gradient, representative of (1) mixed medium-density residential housing and (2) agriculture. These sites have overlapping δ15N and δ18O measurements in NO3– and are unable to discriminate between different N sources. Boron isotopes and concentrations are measurably different between the two sites, with little overlap. The subterranean estuary impacted by mixed medium-density residential housing shows little correlation between δ11B and [B] or between δ11B and salinity, demonstrating that direct mixing relationships between fresh groundwater and seawater were unlikely to account for the variability. No two sources could adequately characterize the δ11B of this subterranean estuary. Groundwater N at this location should be derived from individual homeowner cesspools, although measured septic waste has much lower δ11B compared to the coastal groundwaters. This observation, with no trend in δ11B with [B] indicates multiple sources supply B to the coastal groundwaters. The agricultural subterranean estuary displayed a positive correlation between δ11B and [B] without any relationship with salinity. Binary mixing between sea spray and fertilizer can reasonably explain the distribution of B in the agricultural subterranean estuary. Results from this study demonstrate that δ11B can be used in combination with δ15N to trace sources of NO3– to the subterranean estuary if source endmember isotopic signatures are well-constrained, and if the influence of seawater on δ11B signatures can be minimized or easily quantified.
    Description: This research was funded by New York Sea Grant projects R/CMC-13 and R/CMC-13-NYCT. The MC-ICP-MS used for this work was funded through NSF-MRI 0959524.
    Keywords: Submarine groundwater discharge ; Boron ; Nitrogen ; Nitrate ; Fertilizer ; Wastewater ; Septic waste
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 2
    Publication Date: 2022-10-26
    Description: © 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.
    Description: 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.
    Description: 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).
    Keywords: Radium isotopes ; Submarine groundwater discharge ; Porewater exchange ; Nitrogen ; Long Island Sound
    Repository Name: Woods Hole Open Access Server
    Type: Article
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  • 3
    Publication Date: 2022-10-26
    Description: © The Author(s), 2021. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Roca-Marti, M., Puigcorbe, V., Castrillejo, M., Casacuberta, N., Garcia-Orellana, J., Kirk Cochran, J., & Masque, P. Quantifying Po-210/Pb-210 disequilibrium in seawater: a comparison of two precipitation methods with differing results. Frontiers in Marine Science, 8, (2021): 684484, https://doi.org/10.3389/fmars.2021.684484.
    Description: The disequilibrium between lead-210 (210Pb) and polonium-210 (210Po) is increasingly used in oceanography to quantify particulate organic carbon (POC) export from the upper ocean. This proxy is based on the deficits of 210Po typically observed in the upper water column due to the preferential removal of 210Po relative to 210Pb by sinking particles. Yet, a number of studies have reported unexpected large 210Po deficits in the deep ocean indicating scavenging of 210Po despite its radioactive mean life of ∼ 200 days. Two precipitation methods, Fe(OH)3 and Co-APDC, are typically used to concentrate Pb and Po from seawater samples, and deep 210Po deficits raise the question whether this feature is biogeochemically consistent or there is a methodological issue. Here, we present a compilation of 210Pb and 210Po studies that suggests that 210Po deficits at depths 〉300 m are more often observed in studies where Fe(OH)3 is used to precipitate Pb and Po from seawater, than in those using Co-APDC (in 68 versus 33% of the profiles analyzed for each method, respectively). In order to test whether 210Po/210Pb disequilibrium can be partly related to a methodological artifact, we directly compared the total activities of 210Pb and 210Po in four duplicate ocean depth-profiles determined by using Fe(OH)3 and Co-APDC on unfiltered seawater samples. While both methods produced the same 210Pb activities, results from the Co-APDC method showed equilibrium between 210Pb and 210Po below 100 m, whereas the Fe(OH)3 method resulted in activities of 210Po significantly lower than 210Pb throughout the entire water column. These results show that 210Po deficits in deep waters, but also in the upper ocean, may be greater when calculated using a commonly used Fe(OH)3 protocol. This finding has potential implications for the use of the 210Po/210Pb pair as a tracer of particle export in the oceans because 210Po (and thus POC) fluxes calculated using Fe(OH)3 on unfiltered seawater samples may be overestimated. Recommendations for future research are provided based on the possible reasons for the discrepancy in 210Po activities between both analytical methods.
    Description: MR-M was supported by an Endeavour Research Fellowship (6054) from the Australian Government, the Woods Hole Oceanographic Institution’s Ocean Twilight Zone study, and the Ocean Frontier Institute. VP received funding from the Edith Cowan University under the Early Career Researcher Grant Scheme (G1003456) and the Collaboration Enhancement Scheme (G1003362). MC is currently funded by an ETH Zurich Postdoctoral Fellowship Program (17-2 FEL-30), co-funded by the Marie Curie Actions for People COFUND Program. Support to JKC was provided by the National Science Foundation grant OCE-1736591. The authors acknowledge the financial support from the Spanish Ministry of Science, Innovation and Universities through the “María de Maeztu” program for Units of Excellence (CEX2019-000940-M), the Australian Research Council LIEF Project (LE170100219), and the Generalitat de Catalunya (MERS; 2017 SGR-1588).
    Keywords: Marine chemistry ; Radiochemistry ; Polonium isotopes ; Precipitation methods ; Co-APDC ; Fe(OH)3 ; 210Po/210Pb disequilibrium
    Repository Name: Woods Hole Open Access Server
    Type: Article
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