The recent history and future of the subterranean estuary

During the past century, anthropogenic forces changed the composition of water in coastal aquifers. These changes were brought about by excessive mining of coastal groundwater, dredging and pier construction, wetland draining, and hard surface expansion. These forces caused an increase of salinity in the subterranean estuary, which led to a series of biogeochemical reactions. These changes continue today

Shelf-basin interactions and water mass residence times in the western Arctic Ocean: Insights provided by radium isotopes

Author Posting. © American Geophysical Union, 2019. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research-Oceans 124(5), (2019): 3279-3297, doi: 10.1029/2019JC014988.Radium isotopes are produced through the decay of thorium in sediments and are soluble in seawater; thus, they are useful for tracing ocean boundary‐derived inputs to the ocean. Here we apply radium isotopes to study continental inputs and water residence times in the Arctic Ocean, where land‐ocean interactions are currently changing in response to rising air and sea temperatures. We present the distributions of radium isotopes measured on the 2015 U.S. GEOTRACES transect in the Western Arctic Ocean and combine this data set with historical radium observations in the Chukchi Sea and Canada Basin. The highest activities of radium‐228 were observed in the Transpolar Drift and the Chukchi shelfbreak jet, signaling that these currents are heavily influenced by interactions with shelf sediments. The ventilation of the halocline with respect to inputs from the Chukchi shelf occurs on time scales of ≤19–23 years. Intermediate water ventilation time scales for the Makarov and Canada Basins were determined to be ~20 and >30 years, respectively, while deep water residence times in these basins were on the order of centuries. The radium distributions and residence times described in this study serve as a baseline for future studies investigating the impacts of climate change on the Arctic Ocean.We thank the captain and crew of the USCGC Healy (HLY1502) and the chief scientists D. Kadko and W. Landing for coordinating a safe and successful expedition. We thank the members of the pump team, P. Lam, E. Black, S. Pike, X. Yang, and M. Heller for their assistance with sample collection and for their unfailingly positive attitudes during this 65‐day expedition. We also appreciate sampling assistance from P. Aguilar and M. Stephens, and MATLAB assistance from B. Corlett, A. Pacini, P. Lin, and M. Li. The radium data from the HLY1502 expedition are available through the Biological & Chemical Oceanography Data Management Office (https://www.bco‐dmo.org/dataset/718440) and the radium measurements from the SHEBA, AWS‐2000, and SBI expeditions can be found in the supporting information. This work was funded by NSF awards OCE‐1458305 to M.A.C., OCE‐1458424 to W.S.M., and PLR‐1504333 to R.S.P. This research was conducted with Government support under and awarded by a DoD, Air Force Office of Scientific Research, National Defense Science and Engineering Graduate (NDSEG) Fellowship awarded to L.E.K., 32 CFR 168a.2019-10-2

Observational and modeling evidence of seasonal trends in sediment-derived material inputs to the Chukchi Sea

Author Posting. © American Geophysical Union, 2020. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Journal of Geophysical Research: Oceans 125(5), (2020): e2019JC016007, doi:10.1029/2019JC016007.Benthic inputs of nutrients help support primary production in the Chukchi Sea and produce nutrient‐rich water masses that ventilate the halocline of the western Arctic Ocean. However, the complex biological and redox cycling of nutrients and trace metals make it difficult to directly monitor their benthic fluxes. In this study, we use radium‐228, which is a soluble radionuclide produced in sediments, and a numerical model of an inert, generic sediment‐derived tracer to study variability in sediment inputs to the Chukchi Sea. The 228Ra observations and modeling results are in general agreement and provide evidence of strong benthic inputs to the southern Chukchi Sea during the winter, while the northern shelf receives higher concentrations of sediment‐sourced materials in the spring and summer due to continued sediment‐water exchange as the water mass traverses the shelf. The highest tracer concentrations are observed near the shelfbreak and southeast of Hanna Shoal, a region known for high biological productivity and enhanced benthic biomass.This study presents data from multiple Arctic expeditions over the past two decades, and we are indebted to the captains, crews, and scientific parties that made this data collection possible. This work was funded by NSF awards OCE‐1458305 to M. Charette, OCE‐1458424 to W. Moore, OCE‐1434085 to D. Kadko, PLR‐1504333 to R. Pickart, and OPP‐1822334 to M. Spall. Funding was also provided by National Oceanic and Atmospheric Administration Grant NA14‐OAR4320158 to R. Pickart. L. Kipp was supported by an Ocean Frontier Institute Postdoctoral Fellowship. Radium data used in this manuscript are available in Table S1.2020-10-2

Erratum : GEOTRACES radium isotopes interlaboratory comparison experiment

Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography: Methods 10 (2012): 617, doi:10.4319/lom.2012.10.617.In our original paper, Charette, M. A., H. Dulaiova, M. E. Gonneea, P. B. Henderson, W. S. Moore, J. C. Scholten, and M. K. Pham. 2012. GEOTRACES radium isotopes interlaboratory comparison experiment. Limonol. Oceanogr.: Methods 10:451, the incorrect headers were used for Table 9

GEOTRACES radium isotopes interlaboratory comparison experiment

Author Posting. © Association for the Sciences of Limnology and Oceanography, 2012. This article is posted here by permission of Association for the Sciences of Limnology and Oceanography for personal use, not for redistribution. The definitive version was published in Limnology and Oceanography: Methods 10 (2012): 451-463, doi:10.4319/lom.2012.10.451.In anticipation of the international GEOTRACES program, which will study the global marine biogeochemistry of trace elements and isotopes, we conducted a multi-lab intercomparison for radium isotopes. The intercomparison was in two parts involving the distribution of: (1) samples collected from four marine environments (open ocean, continental slope, shelf, and estuary) and (2) a suite of four reference materials prepared with isotopic standards (circulated to participants as 'unknowns'). Most labs performed well with 228Ra and 224Ra determination, however, there were a number of participants that reported 226Ra, 223Ra, and 228Th (supported 224Ra) well outside the 95% confidence interval. Many outliers were suspected to be a result of poorly calibrated detectors, though other method specific factors likely played a role (e.g., detector leakage, insufficient equilibration). Most methods for radium analysis in seawater involve a MnO2 fiber column preconcentration step; as such, we evaluated the extraction efficiency of this procedure and found that it ranged from an average of 87% to 94% for the four stations. Hence, nonquantitative radium recovery from seawater samples may also have played a role in lab-to-lab variability.This work was funded by grants from the National Science Foundation (OCE- 0751461to M.A.C and H.D. and OCE- 0751867 to W.S.M.)

Tracing the Mixing and Movement of Groundwater into Florida Bay with Four Naturally Occurring Radium Isotopes

Proceedings of the 1999 Georgia Water Resources Conference, March 30 and 31, Athens, Georgia.Four naturally occurring isotopes of radium (²²³, ²²⁴, ²²⁶, ²²⁸Ra) have a range in half-life that extends from a few days to over 1,600 years. Unique geochemical attributes make these radium isotopes ideal to examine sediment/water interface exchange processes in coastal waters. Here we present initial radium isotopic data of Florida Bay, a heavily impacted coastal system in south Florida. Florida Bay is a shallow, brackish, semi-enclosed water body that receives most of its limited freshwater supply from the Everglades, principally by surficial water runoff through Trout Creek/Taylor River. Because the entire region is underlain by highly porous Key Largo limestone and due to other hydrologic constraints, there is the possibility that ground water exchange may be significant in Florida Bay. To evaluate the extent of such a subsurface contribution, radium isotopes are being determined in shallow wells, seepage meter sites, and a series of water column samples across the Everglades National Park-Florida Bay boundary. All four radium isotopes were at least an order of magnitude greater in the two shallow well samples than in the water column samples. For example, ²²⁶Ra ranged from about 0.50 dpm L⁻¹ at a salinity of 5 to over 13 dpm L⁻¹ in Well B (salinity = 47.2). Isotopic radium ratios reveal that the well waters (i.e., marine ground water) are geochemically distinct from surficial waters and are regenerated on a time-scale of several days (i.e., ²²⁴Ra/²²³Ra). Results indicate that this radium quartet can be used effectively in Florida Bay to examine the exchange of surficial water and ground water.Sponsored and Organized by: U.S. Geological Survey, Georgia Department of Natural Resources, The University of Georgia, Georgia State University, Georgia Institute of TechnologyThis book was published by the Institute of Ecology, The University of Georgia, Athens, Georgia 30602-2202 with partial funding provided by the U.S. Department of Interior, geological Survey, through the Georgia Water Research Insttitute as authorized by the Water Research Institutes Authorization Act of 1990 (P.L. 101-397). The views and statements advanced in this publication are solely those of the authors and do not represent official views or policies of the University of Georgia or the U.S. Geological Survey or the conference sponsors

Global estimate of submarine groundwater discharge based on an observationally constrained radium isotope model

© The Author(s), 2014. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Geophysical Research Letters 41 (2014): 8438–8444, doi:10.1002/2014GL061574.Along the continental margins, rivers and submarine groundwater supply nutrients, trace elements, and radionuclides to the coastal ocean, supporting coastal ecosystems and, increasingly, causing harmful algal blooms and eutrophication. While the global magnitude of gauged riverine water discharge is well known, the magnitude of submarine groundwater discharge (SGD) is poorly constrained. Using an inverse model combined with a global compilation of 228Ra observations, we show that the SGD integrated over the Atlantic and Indo-Pacific Oceans between 60°S and 70°N is (12 ± 3) × 1013 m3 yr−1, which is 3 to 4 times greater than the freshwater fluxes into the oceans by rivers. Unlike the rivers, where more than half of the total flux is discharged into the Atlantic, about 70% of SGD flows into the Indo-Pacific Oceans. We suggest that SGD is the dominant pathway for dissolved terrestrial materials to the global ocean, and this necessitates revisions for the budgets of chemical elements including carbon.This work was supported by the Ministry of Oceans and Fisheries, Korea, through the Korea Institute of Marine Science and Technology (KIMST) (20120176) and National Research Foundation (NRF) of Korea (2013R1A2A1A05004343 and 2013R1A1A1058203). Charette and Moore's contributions were supported by the US National Science Foundation through the GEOTRACES project

The release of dissolved actinium to the ocean : A global comparison of different end-members

Author Posting. © Elsevier B.V., 2007. 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 Marine Chemistry 109 (2008): 409-420, doi:10.1016/j.marchem.2007.07.005.The measurement of short-lived 223Ra often involves a second measurement for supported activities, which represents 227Ac in the sample. Here we exploit this fact, presenting a set of 284 values on the oceanic distribution of 227Ac, which was collected when analyzing water samples for short-lived radium isotopes by the radium delayed coincidence counting system. The present work compiles 227Ac data from coastal regions all over the northern hemisphere, including values from ground water, from estuaries and lagoons, and from marine endmembers. Deep-sea samples from a continental slope off Puerto Rico and from an active vent site near Hawaii complete the overview of 227Ac near its potential sources. The average 227Ac activities of nearshore marine end-members range from 0.4 dpm * m-3 at the Gulf of Mexico to 3.0 dpm *m-3 in the coastal waters of the Korean Strait. In analogy to 228Ra, we find the extension of adjacent shelf regions to play a substantial role for 227Ac activities, although less pronounced than for radium, due to its weaker shelf source. Based on previously published values, we calculate an open ocean 227Ac inventory of 1.35 * 1018 dpm 227Acex in the ocean, which corresponds to 37 moles, or 8.4 kg. This implies a flux of 127 dpm*m-2*y-1 from the deep-sea floor. For the shelf regions, we obtain a global inventory of 227Ac of 4.5 * 1015 dpm, which cannot be converted directly into a flux value, as the regional loss term of 227Ac to the open ocean would have to be included. Ac has so far been considered to behave similarly to Ra in the marine environment, with the exception of a strong Ac source in the deep-sea due to 231Paex. Here, we present evidence of geochemical differences between Ac, which is retained in a warm vent system, and Ra, which is readily released (Moore et al., submitted). Another potential mechanism of producing deviations in 227Ac/228Ra and daughter isotope ratios from the expected production value of lithogenic material is observed at reducing environments, where enrichment in uranium may occur. The presented data here may serve as a reference for including 227Ac in circulation models, and the overview provides values for some end-members that contribute to the global Ac distribution