210Po and 210Pb distributions during a phytoplankton bloom in the North Atlantic: Implications for POC export

© The Author(s), 2020. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Horowitz, E. J., Cochran, J. K., Bacon, M. P., & Hirschberg, D. J. 210Po and 210Pb distributions during a phytoplankton bloom in the North Atlantic: implications for POC export. Deep-Sea Research Part I: Oceanographic Research Papers, 164, (2020): 103339, doi:10.1016/j.dsr.2020.103339.During the North Atlantic Bloom Experiment (NABE) of the Joint Global Ocean Flux Study (JGOFS), water column sampling for particulate and dissolved 210Po and 210Pb was performed four times (26 April and 4, 20, 30 May 1989) during a month-long Lagrangian time-series occupation of the NABE site, as well as one-time samplings at stations during transit to and from the site. There are few prior studies documenting short-term changes in 210Po and 210Pb profiles over the course of a phytoplankton bloom, and we interpret the profiles in terms of the classical “steady-state” (SS) approach used in most studies, as well as by using a non-steady state approach suggested by the temporal evolution of the profiles. Changes in 210Po profiles during a bloom are expectable as this radionuclide is scavenged and exported. During NABE, 210Pb profiles also displayed non-steady state, with significant increases in upper water column inventory occurring midway through the experiment. Export of 210Po from the upper 150 m using the classic “steady-state” model shows increases from 0.5 ± 8.5 dpm m−2 d−1 to 68.2 ± 4.2 dpm m−2 d−1 over the ~one-month occupation. Application of a non-steady state model, including changes in both 210Pb and 210Po profiles, gives higher 210Po export fluxes. Detailed depth profiles of particulate organic carbon (>0.8 μm) and particulate 210Po (>0.4 μm) are available from the 20 and 30 May samplings and show maxima in POC/Po at ~37 m. Applying the POC/210Po ratios at 150 m to the “steady state” 210Po fluxes yields POC export from the upper 150 m of 8.2 ± 1.5 mmol C m− 2 d−1 on 20 May and 6.0 ± 1.6 mmol C m−2 d−1 on 30 May. The non-steady state model applied to the interval 20 to 30 May yields POC export of 24.3 mmol C m−2 d−1. The non-steady state (NSS) 210Po-derived POC fluxes are comparable to, but somewhat less than, those estimated previously from 234Th/238U disequilibrium for the same time interval (37.3 and 45.0 mmol m−2 d−1, depending on the POC/Th ratio used). In comparison, POC fluxes measured with a floating sediment trap deployed at 150 m from 20 to 30 May were 11.6 mmol m−2 d−1. These results suggest that non-steady state Po-derived POC fluxes during the NABE agree well with those derived from 234Th/238U disequilibrium and agree with sediment trap fluxes within a factor of ~2. However, unlike the 234Th-POC flux proxy, non-steady stage changes in profiles of 210Pb, the precursor of 210Po, must be considered.We are grateful to T. Hammar and A. Fleer (WHOI) for assistance at sea and in the laboratory. This work was supported originally by National Science Foundation (United States) grant OCE-8819544 to JKC and more recently by OCE-1736591. We thank Stephen Thurston (American Museum of Natural History) for graphics assistance Robert Aller, Steven Beaupre, and two anonymous reviewers for helpful comments

Identification and quantification of diffuse fresh submarine groundwater discharge via airborne thermal infrared remote sensing

Airborne thermal infrared (TIR) overflights were combined with shoreline radionuclide surveys to investigate submarine groundwater discharge (SGD) along the north shore of Long Island, NY between June 2013 and September 2014. Regression equations developed for three distinct geomorphological environments suggest a positive linear relationship between the rate of diffuse SGD and the spatial extent of the observed coastal TIR anomalies; such a relationship provides quantitative evidence of the ability to use TIR remote sensing as a tool to remotely identify and measure SGD. Landsat TIR scenes were unable to resolve any of the 18 TIR anomalies identified during the various airborne overflights. Two locations were studied in greater detail via 222Rn time series and manual seepage meters in order to understand why specific shoreline segments did not exhibit a TIR anomaly. SGD at the first site, located within a large, diffuse TIR anomaly, was composed of a mixture of fresh groundwater and circulated seawater with elevated levels of nitrate. In contrast, SGD at the second site, where no coastal TIR anomaly was observed, was composed of circulated seawater with negligible nitrate. Despite the compositional differences in seepage, both sites were similar in discharge magnitude, with average time series 222Rn derived SGD rates equal to 18 and 8 cm d−1 for the TIR site and non-TIR site, respectively. Results suggest that TIR remote sensing has the ability to identify locations of a mixture between diffuse fresh and circulated seawater SGD. If TIR anomalies can be demonstrated to represent a mixture between fresh and circulated seawater SGD, then the cumulative area of the TIR anomalies may be used to estimate the fresh fraction of SGD relative to the cumulative area of the seepage face, and thus allows for improved SGD derived nutrient flux calculations on a regional scale

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

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)

Quantifying 210Po/210Pb disequilibrium in seawater: A comparison of two precipitation methods with differing results

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 \u3e 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

Homotopy on spatial graphs and generalized Sato-Levine invariants

Edge-homotopy and vertex-homotopy are equivalence relations on spatial graphs which are generalizations of Milnor's link-homotopy. Fleming and the author introduced some edge (resp. vertex)-homotopy invariants of spatial graphs by applying the Sato-Levine invariant for the constituent 2-component algebraically split links. In this paper, we construct some new edge (resp. vertex)-homotopy invariants of spatial graphs without any restriction of linking numbers of the constituent 2-component links by applying the generalized Sato-Levine invariant.Comment: 16 pages, 13 figure

Temporal variability of lagoon–sea water exchange and seawater circulation through a Mediterranean barrier beach

The subterranean flow of water through sand barriers between coastal lagoons and the sea, driven by a positive hydraulic gradient, is a net new pathway for solute transfer to the sea. On the sea side of sand barriers, seawater circulation in the swash-zone generates a flux of recycled and new solutes. The significance and temporal variability of these vectors to the French Mediterranean Sea is unknown, despite lagoons constituting ~ 50% of the coastline. A one-dimensional 224Raex/223Ra reactive-transport model was used to quantify water flow between a coastal lagoon (La Palme) and the sea over a 6-month period. Horizontal flow between the lagoon and sea decreased from ~ 85 cm d−1 during May 2017 (0.3 m3 d−1 m−1 of shoreline) to ~ 20 cm d−1 in July and was negligible in the summer months thereafter due to a decreasing hydraulic gradient. Seawater circulation in the swash-zone varied from 10 to 52 cm d−1 (0.4–2.1 m3 d−1 m−1), driven by short-term changes in the prevailing wind and wave regimes. Both flow paths supply minor dissolved silica fluxes on the order of ~ 3–10 mmol Si d−1 m−1. Lagoon–sea water exchange supplies a net dissolved inorganic carbon (DIC) flux (320–1100 mmol C d−1 m−1) two orders of magnitude greater than seawater circulation and may impact coastal ocean acidification. The subterranean flow of water through sand barriers represents a significant source of new DIC, and potentially other solutes, to the Mediterranean Sea during high lagoon water-level periods and should be considered in seasonal element budgets

Glacial controls on redox-sensitive trace element cycling in Arctic fjord sediments (Spitsbergen, Svalbard)

Glacial meltwater is an important source of bioessential trace elements to high latitude oceans. Upon delivery to coastal waters, glacially sourced particulate trace elements are processed during early diagenesis in sediments and may be sequestered or recycled back to the water column depending on local biogeochemical conditions. In the glaciated fjords of Svalbard, large amounts of reactive Fe and Mn (oxyhydr)oxides are delivered to the sediment by glacial discharge, resulting in pronounced Fe and Mn cycling concurrent with microbial sulfate reduction. In order to investigate the diagenetic cycling of selected trace elements (As, Co, Cu, Mo, Ni, and U) in this system, we collected sediment cores from two Svalbard fjords, Van Keulenfjorden and Van Mijenfjorden, in a transect along the head-to-mouth fjord axis and analyzed aqueous and solid phase geochemistry with respect to trace elements, sulfur, and carbon along with sulfate reduction rates. We found that Co and Ni associate with Fe and Mn (oxyhydr)oxides and enter the pore water upon reductive metal oxide dissolution. Copper is enriched in the solid phase where sulfate reduction rates are high, likely due to reactions with H2S and the formation of sulfide minerals. Uranium accumulates in the solid phase likely following reduction by both Fe- and sulfate-reducing bacteria, while Mo adsorbs to Fe and Mn (oxyhydr)oxides in the surface sediment and is removed from the pore water at depth where sulfidization makes it particle-reactive. Arsenic is tightly coupled to Fe redox cycling and its partitioning between solid and dissolved phases is influenced by competition with FeS for adsorption sites on crystalline Fe oxides. Differences in trace element cycling between the two fjords suggest delivery of varying amount and composition of tidewater glacier (Van Keulenfjorden) and meltwater stream (Van Mijenfjorden) material, likely related to oxidative processes occurring in meltwater streams. This processing produces a partially weathered, more reactive sediment that is subject to stronger redox cycling of Fe, Mn, S, and associated trace elements upon delivery to Van Mijenfjorden. With climate warming, the patterns of trace element cycling observed in Van Mijenfjorden may also become more prevalent in other Svalbard fjords as tidewater glaciers retreat into meltwater stream valleys