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  • 1
    Publication Date: 2022-05-25
    Description: 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 110 (2008): 120-127, doi:10.1016/j.marchem.2008.02.011.
    Description: Submarine groundwater discharge (SGD), in form of springs and diffuse seepage, has long been recognized as a source of chemical constituents to the coastal ocean. Because groundwater is two to four orders of magnitude richer in radon than surface water, it has been used as both a qualitative and a quantitative tracer of groundwater discharge. Besides this large activity gradient, the other perceived advantage of radon stems from its classification as noble gas; that is, its chemical behavior is expected not to be influenced by salinity, redox, and diagenetic conditions present in aquatic environments. During our three-year monthly sampling of the subterranean estuary (STE) in Waquoit Bay, MA, we found highly variable radon activities (50-1600 dpm L-1) across the fresh-saline interface of the aquifer. We monitored pore water chemistry and radon activity at 8 fixed depths spanning from 2 to 5.6 m across the STE, and found seasonal fluctuations in activity at depths where elevated radon was observed. We postulate that most of pore water 222Rn is produced from particle-surface bound 226Ra, and that the accumulation of this radium is likely regulated by the presence of manganese (hydr)oxides. Layers of manganese (hydr)oxides form at the salinity transition zone (STZ), where water with high salinity, high manganese, and low redox potential mixes with fresh water. Responding to the seasonality of aquifer recharge, the location of the STZ and the layers with radium enriched manganese (hydr)oxide follows the seasonal land- or bay-ward movement of the freshwater lens. This results in seasonal changes in the depth where elevated radon activities are observed. The conclusion of our study is that the freshwater part of the STE has a radon signature that is completely different from the STZ or recirculated sea water. Therefore, the radon activity in SGD will depend on the ratio of fresh and recirculated seawater in the discharging groundwater.
    Description: This work is a result of research sponsored by NSF (OCE- 0425061 to M.A.C.) and the WHOI Postdoctoral Scholar program (to H.D.).
    Keywords: Subterranean estuary ; Geochemical tracers ; Radon ; Radium ; Manganese ; Groundwater ; Submarine groundwater discharge ; Geochemical transformations
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
    Format: application/pdf
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  • 2
    Publication Date: 2022-05-26
    Description: 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): 250-267, doi:10.1016/j.marchem.2007.12.002.
    Description: Over the past decade, radium isotopes have been frequently applied as tracers of submarine groundwater discharge (SGD). The unique radium signature of SGD is acquired within the subterranean estuary, a mixing zone between fresh groundwater and seawater in coastal aquifers, yet little is known about what controls Ra cycling in this system. The focus of this study was to examine controls on sediment and groundwater radium activities within permeable aquifer sands (Waquoit Bay, MA, USA) through a combination of field and laboratory studies. In the field, a series of sediment cores and corresponding groundwater profiles were collected for analysis of the four radium isotopes, as well as dissolved and sediment associated manganese, iron, and barium. We found that in addition to greater desorption at increasing salinity, radium was also closely tied to manganese and iron redox cycling within these sediments. A series of laboratory adsorption/desorption experiments helped elucidate the importance of 1) contact time between sediment and water, 2) salinity of water in contact with sediment, 3) redox conditions of water in contact with sediment, and 4) the chemical characteristics of sediment on radium adsorption/desorption. We found that these reactions are rapid (on the order of hours), desorption increases with increasing salinity and decreasing pH, and the presence of Fe and Mn (hydr)oxides on the sediment inhibit the release of radium. These sediments have a large capacity to sorb radium from fresh water. Combined with these experimental results, we present evidence from time series groundwater sampling that within this subterranean estuary there are cyclic periods of Ra accumulation and release controlled by changing salinity and redox conditions.
    Description: This work is a result of research sponsored by NSF (OCE- 0425061 to M.A.C.), the WHOI-NOC Student Exchange program (to P.J.M), and the WHOI Postdoctoral Scholar program (to H.D.).
    Keywords: Radium ; Sediments ; Desorption ; Adsorption ; Barium ; Submarine groundwater ; Subterranean estuary ; Redox reactions ; Ion exchange ; Distribution coefficient
    Repository Name: Woods Hole Open Access Server
    Type: Preprint
    Format: application/pdf
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