Description: MedFlux sampling was carried out at the French JGOFS DYFAMED (DYnamique des Flux Atmospheriques en MEDiterranee) site in the Ligurian Sea (northwestern Mediterranean), 52km off Nice (431200N, 71400E) in 2300m water depth. In 2003, a mooring with sediment trap arrays was deployed 6 March (day of year, DOY 65) and recovered 6 May (DOY 126); this trap deployment will be referred to as Period 1 (P1). The array was redeployed a week later on 14 May (DOY 134) and recovered again on 30 June (DOY 181); this trap deployment will be referred to as Period 2 (P2). Indented-rotating sphere (IRS) valve traps were fitted with TS carousels to determine temporal variability of particulate matter flux. TS traps were fitted with ''dimpled'' spheres. Vertical flux at 200m depth is considered to be equivalent to new or export production, and traps sampled at 238 and 117m during P1 and P2, respectively. We also collected TS material at 711m during P1 and at 1918m during P2. Upon recovery, samples were split using a McLaneTM WSD splitter to allow multiple chemical analyses. Here we report 2003 data on TS particulate mass, and the contributions of organic carbon (OC), opal, lithogenic material and calcium carbonate to mass. In 2005, traps were deployed as described above for 55 d during a single period from 4 March (DOY 63) to 1 May (DOY 121). TS traps were fitted with ''dimpled'' spheres. TS particulate matter was collected from 313 to 924 m.

Description: Author Posting. © The Author(s), 2013. This is the author's version of the work. It is posted here by permission of Elsevier B.V. for personal use, not for redistribution. The definitive version was published in Geochimica et Cosmochimica Acta 117 (2013): 33-52, doi:10.1016/j.gca.2013.03.021.

Description: Submarine groundwater discharge (SGD) to the ocean supplies Sr with less radiogenic 87Sr/86Sr than seawater, and thus constitutes an important term in the Sr isotope budget in the modern ocean. However, few data exist for Sr in coastal groundwater or in the geochemically dynamic subterranean estuary (STE). We examined Sr concentrations and isotope ratios from nine globally-distributed coastal sites and characterized the behavior of Sr in the STE. Dissolved Sr generally mixed conservatively in the STE, although large differences were observed in the meteoric groundwater end-member Sr concentrations among sites (0.1 – 24 μM Sr). Strontium isotope exchange was observed in the STE at five of the sites studied, and invariably favored the meteoric groundwater end-member signature. Most of the observed isotope exchange occurred in the salinity range 5-15, and reached up to 40% exchange at salinity 10. Differences in fresh groundwater Sr concentrations and isotope ratios (87Sr/86Sr = 0.707-0.710) reflected aquifer lithology. The SGD end-member 87Sr/86Sr must be lower than modern seawater (i.e., less than 0.70916) in part because groundwater Sr concentrations are orders of magnitude higher in less-carbonate and volcanic island aquifers. A simple lithological model and groundwater Sr data compiled from the literature were used to estimate a global average groundwater end-member of 2.9 μM Sr with 87Sr/86Sr = 0.7089. This represents a meteoric-SGD-driven Sr input to the ocean of 0.7-2.8 × 1010 mol Sr y-1. Meteoric SGD therefore accounts for 2-8% of the oceanic Sr isotope budget, comparable to other known source terms, but is insufficient to balance the remainder of the budget. Using reported estimates for brackish SGD, the estimated volume discharge at salinity 10 (7-11 × 1015 L y-1) was used to evaluate the impact of isotope exchange in the STE on the brackish SGD Sr flux. A moderate estimate of 25% isotope exchange in the STE gives an SGD Sr end-member 87Sr/86Sr of 0.7091. The brackish SGD Sr flux thus accounts for 11-23% of the marine Sr isotope budget, but does not appear sufficient to balance the ~40% remaining after other known sources are included. Substantial uncertainties remain for estimating the SGD source of Sr to the global ocean, especially in the determination of the volume flux of meteoric SGD, and in the paucity of measurements of groundwater Sr isotope composition in major SGD regions such as Papua New Guinea, the South America west coast, and West Africa. Consequently, our global estimate should be viewed with some caution. Nevertheless, we show that the combined sources of meteoric SGD and brackish SGD coupled with isotope exchange in the STE may constitute a substantial component (~13-30%) of the modern oceanic 87Sr/86Sr budget, likely exceeding less radiogenic Sr inputs by sedimentary diagenesis and hydrothermal circulation through the mid-ocean ridge system. Temporal variation in SGD Sr fluxes and isotope composition may have contributed to fluctuations in the oceanic 87Sr/86Sr ratio over geologic time.

Description: This project was supported by funding from the WHOI Coastal Ocean 670 Institute and the Tropical Research Initiative, and NSF OCE-0751525 to MAC. BPE acknowledges financial support from NSF ETBC-85101500 and a WHOI Coastal Ocean Institute Fellowship.

Description: © 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.

Description: 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.

Description: 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.

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).

Description: Dataset: GP15 210Po and 210Pb Aerosols Leg 2

Description: This dataset includes activities of 210Po (Polonium-210) and 210Pb (Lead-210) in aerosol samples collected on Leg 2 (Hilo, HI to Papeete, French Polynesia) of the US GEOTRACES Pacific Meridional Transect (PMT) cruise (GP15, RR1815) on R/V Roger Revelle from October to November 2018 For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/878703

Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1736591, NSF Division of Ocean Sciences (NSF OCE) OCE-1736612

Description: Dataset: GP15 210Po and 210Pb Aerosols Leg 1

Description: This dataset includes activities of 210Po (Polonium-210) and 210Pb (Lead-210) in aerosol samples collected on Leg 1 (Seattle, WA to Hilo, HI) of the US GEOTRACES Pacific Meridional Transect (PMT) cruise (GP15, RR1814) on R/V Roger Revelle from September to October 2018. For a complete list of measurements, refer to the full dataset description in the supplemental file 'Dataset_description.pdf'. The most current version of this dataset is available at: https://www.bco-dmo.org/dataset/878689

Description: NSF Division of Ocean Sciences (NSF OCE) OCE-1736591, NSF Division of Ocean Sciences (NSF OCE) OCE-1736612

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.

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).

Description: Methane seep deposits are common in the Upper Cretaceous Pierre Shale of the U.S. Western Interior. They contain a rich fauna including ammonites, bivalves, gastropods, sponges, corals, echinoids, crinoids, and fish. In an effort to understand the role of ammonites in these ecosystems, we examined a seep from the upper Campanian Didymoceras cheyennense Zone in Custer County, South Dakota, that contains molluscs with well-preserved shell material permitting isotopic analyses. Values of δ13C of the micritic limestone at the seep range from −46.94‰ to −11.49‰, confirming the influence of anaerobic oxidation of methane on the isotopic composition of the dissolved inorganic carbon reservoir. The ammonites also consistently display light values of δ13C ranging from −13.71‰ to 0.68‰. These values are generally lighter than those in nonseep specimens from age-equivalent rocks elsewhere in the basin (–1.75‰ to 3.42‰). In a single specimen of Baculites corrugatus from the seep, light δ13C values occur throughout ontogeny. These data suggest that ammonites incorporated isotopically light methane-derived carbon in their shells and lived near the vent fluids and methane-oxidizing bacteria. Both juvenile and adult specimens are present, implying that these ammonites spent their entire lives at the seep and formed an integral part of an interwoven community. The values of 87Sr/86Sr in the limestone and well-preserved fossils at the seep (0.707690–0.707728) are higher than that of the open ocean at this time (0.707659). These elevated values suggest that the seep fluids were imprinted with a radiogenic Sr signature, perhaps derived from equilibration with granitic deposits at depth during the initial uplift of the Black Hills.