Geochemical and physical sources of radon variation in a subterranean estuary — implications for groundwater radon activities in submarine groundwater discharge studies

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.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.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.)

Natural iron enrichment around the Antarctic Peninsula in the Southern Ocean

As part of the US-AMLR program in January-February of 2006, 99 stations in the South Shetland Islands-Antarctic Peninsula region were sampled to understand the variability in hydrographic and biological properties related to the abundance and distribution of krill in this area. Concentrations of dissolved iron (DFe) and total acid-leachable iron (TaLFe) were measured in the upper 150 m at 16 of these stations (both coastal and pelagic waters) to better resolve the factors limiting primary production in this area and in downstream waters of the Scotia Sea. The concentrations of DFe and TaLFe in the upper mixed layer (UML) were relatively high in Weddell Sea Shelf Waters (~0.6 nM and 15 nM, respectively) and low in Drake Passage waters (~0.2 nM and 0.9 nM, respectively). In the Bransfield Strait, representing a mixture of waters from the Weddell Sea and the Antarctic Circumpolar Current (ACC), concentrations of DFe were ~0.4 nM and of TaLFe ~1.7 nM. The highest concentrations of DFe and TaLFe in the UML were found at shallow coastal stations close to Livingston Island (~1.6 nM and 100 nM, respectively). The ratio of TaLFe:DFe varied with the distance to land: ~45 at the shallow coastal stations, ~15 in the high-salinity waters of Bransfield Strait, and ~4 in ACC waters. Concentrations of DFe increased slightly with depth in the water column, while that of TaLFe did not show any consistent trend with depth. Our Fe data are discussed in regard to the hydrography and water circulation patterns in the study area, and with the hypothesis that the relatively high rates of primary production in the central regions of the Scotia Sea are partially sustained by natural iron enrichment resulting from a northeasterly flow of iron-rich coastal waters originating in the South Shetland Islands-Antarctic Peninsula region

A new method for the determination of low-level actinium-227 in geological samples

Author Posting. © The Author(s), 2012. This is the author's version of the work. It is posted here by permission of Springer for personal use, not for redistribution. The definitive version was published in Journal of Radioanalytical and Nuclear Chemistry 296 (2013): 279-283, doi:10.1007/s10967-012-2140-0.We developed a new method for the determination of 227Ac in geological samples. The method uses extraction chromatographic techniques and alpha-spectrometry and is applicable for a range of natural matrices. Here we report on the procedure and results of the analysis of water (fresh and seawater) and rock samples. Water samples were acidified and rock samples underwent total dissolution via acid leaching. A DGA (N,N,N’,N’-tetra-n-octyldiglycolamide) extraction chromatographic column was used for the separation of actinium. The actinium fraction was prepared for alpha spectrometric measurement via cerium fluoride micro-precipitation. Recoveries of actinium in water samples were 80±8 % (number of analyses n=14) and in rock samples 70±12 % (n=30). The minimum detectable activities (MDA) were 0.017-0.5 Bq kg-1 for both matrices. Rock sample 227Ac activities ranged from 0.17 to 8.3 Bq kg-1 and water sample activities ranged from below MDA values to 14 Bq kg-1of 227Ac. From the analysis of several standard rock and water samples with the method we found very good agreement between our results and certified values

Assessment of groundwater discharges into West Neck Bay, New York, via natural tracers

Author Posting. © Elsevier B.V., 2006. 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 Continental Shelf Research 29 (2006): 1971-1983, doi:10.1016/j.csr.2006.07.011.A field experiment to compare methods of assessing submarine groundwater discharge (SGD) was held on Shelter Island, NY, in May 2002. We evaluated the use of radon, radium isotopes, and methane to assess SGD rates and dynamics from a glacial aquifer in the coastal zone. Fluxes of radon across the sediment-water interface were calculated from changes in measured surface water inventories following evaluation and correction for tidal effects, atmospheric evasion, and mixing with offshore waters. These fluxes were then converted to SGD rates using the measured radon concentration in the groundwater. We used the short-lived radium isotopes to calculate a horizontal mixing coefficient to assess radon loss by mixing between nearshore and offshore waters. We also made an independent calculation of SGD using the Ra-derived mixing coefficient and the long-lived 226Ra concentration gradient in the bay. Seepage rates were calculated to range between 0 and 34 cm.day-1 using the radon measurements and 15 cm.day-1 as indicated by the radium isotopes. The radiotracer results were consistent and comparable to SGD rates measured directly with vented benthic chambers (seepage meters) deployed during this experiment. These meters indicated rates between 2 and 200 cm.day-1 depending on their location. Both the calculated radon fluxes and rates measured directly by the automated seepage meters revealed a clear reproducible pattern of higher fluxes during low tides. Considering that the two techniques are completely independent, the agreement in the SGD dynamics is significant. Methane concentration in groundwater was very low (~30 nM) and not suitable as SGD tracer at this study site.The SGD intercomparison experiment was partially funded by SCOR, LOICZ, and UNESCO (IOC and IHP). W. C. Burnett acknowledges support from CICEET (Grant# 1368-810-41) and ONR (Grant# 1368-769-27). J. P. Chanton acknowledges support from Seagrant (R\C-E-44). The WHOI researchers acknowledge funding from CICEET (#NA07OR0351, NA17OZ2507)

Shelf-derived iron inputs drive biological productivity in the southern Drake Passage

Author Posting. © American Geophysical Union, 2009. This article is posted here by permission of American Geophysical Union for personal use, not for redistribution. The definitive version was published in Global Biogeochemical Cycles 23 (2009): GB4014, doi:10.1029/2008GB003406.In the Southern Ocean near the Antarctic Peninsula, Antarctic Circumpolar Current (ACC) fronts interact with shelf waters facilitating lateral transport of shelf-derived components such as iron into high-nutrient offshore regions. To trace these shelf-derived components and estimate lateral mixing rates of shelf water, we used naturally occurring radium isotopes. Short-lived radium isotopes were used to quantify the rates of shelf water entrainment while Fe/228Ra ratios were used to calculate the Fe flux. In the summer of 2006 we found rapid mixing and significant lateral iron export, namely, a dissolved iron flux of 1.1 × 105 mol d−1 and total acid leachable iron flux of 1.1 × 106 mol d−1 all of which is transported in the mixed layer from the shelf region offshore. This dissolved iron flux is significant, especially considering that the bloom observed in the offshore region (0.5–2 mg chl a m−3) had an iron demand of 1.1 to 4 × 105 mol Fe. Net vertical export fluxes of particulate Fe derived from 234Th/238U disequilibrium and Fe/234Th ratios accounted for only about 25% of the dissolved iron flux. On the other hand, vertical upward mixing of iron rich deeper waters provided only 7% of the lateral dissolved iron flux. We found that similarly to other studies in iron-fertilized regions of the Southern Ocean, lateral fluxes overwhelm vertical inputs and vertical export from the water column and support significant phytoplankton blooms in the offshore regions of the Drake Passage.This work was funded by the National Science Foundation (ANT-0443869 to M.A.C.)

Isotope tracing of submarine groundwater discharge offshore Ubatuba, Brazil : results of the IAEA–UNESCO SGD project

Author Posting. © Elsevier B.V., 2008. 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 Journal of Environmental Radioactivity 99 (2008): 1596-1610, doi:10.1016/j.jenvrad.2008.06.010.Results of groundwater and seawater analyses for radioactive (3H, 222Rn, 223Ra, 224Ra, 226Ra, 228Ra) and stable (2H, 18O) isotopes are presented together with in situ spatial mapping and time-series 222Rn measurements in seawater, direct seepage measurements using manual and automated seepage meters, pore water investigations using different tracers and piezometric techniques, and geoelectric surveys probing the coast. This study represents first time that such a new complex arsenal of radioactive and non-radioactive tracer techniques and geophysical methods have been used for simultaneous submarine groundwater discharge (SGD) investigations. Large fluctuations of SGD fluxes were observed at sites situated only a few meters apart (from 0 cm d-1 to 360 cm d-1; the unit represents cm3/cm2/day), as well as during a few hours (from 0 cm d-1 to 110 cm d-1), strongly depending on the tidal fluctuations. The average SGD flux estimated from continuous 222Rn measurements is 17±10 cm d-1. Integrated coastal SGD flux estimated for the Ubatuba coast using radium isotopes is about 7x103 m3 d-1 per km of the coast. The isotopic composition (δ2H and δ18O) of submarine waters was characterised by significant variability and heavy isotope enrichment, indicating that the contribution of groundwater in submarine waters varied from a small percentage to 20%. However, this contribution with increasing offshore distance became negligible. Automated seepage meters and time-series measurements of 222Rn activity concentration showed a negative correlation between the SGD rates and tidal stage. This is likely caused by sea level changes as tidal effects induce variations of hydraulic gradients. The geoelectric probing and piezometric measurements contributed to better understanding of the spatial distribution of different water masses present along the coast. The radium isotope data showed scattered distributions with offshore distance, which imply that seawater in a complex coast with many small bays and islands was influenced by local currents and groundwater/seawater mixing. This has also been confirmed by a relatively short residence time of 1-2 weeks for water within 25 km offshore, as obtained by short-lived radium isotopes. The irregular distribution of SGD seen at Ubatuba is a characteristic of fractured rock aquifers, fed by coastal groundwater and recirculated seawater with small admixtures of groundwater, which is of potential environmental concern and has implications on the management of freshwater resources in the region.This research was supported by IAEA and UNESCO (IOC and IHP) in the framework of the joint SGD project. Science support for some U.S. investigators was provided by grants from the National Science Foundation (OCE03-50514 to WCB and OCE02-33657 to WSM)

Isotopic, geophysical and biogeochemical investigation of submarine groundwater discharge : IAEA-UNESCO intercomparison exercise at Mauritius Island

Author Posting. © The Author(s), 2011. 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 Journal of Environmental Radioactivity 104 (2012): 24-45, doi:10.1016/j.jenvrad.2011.09.009.Submarine groundwater discharge (SGD) into a shallow lagoon on the west coast of Mauritius Island (Flic-en-Flac) was investigated using radioactive (3H, 222Rn, 223Ra, 224Ra, 226Ra, 228Ra) and stable (2H, 18O) isotopes and nutrients. SGD intercomparison exercises were carried out to validate the various approaches used to measure SGD including radium and radon measurements, seepage-rate measurements using manual and automated meters, sediment bulk conductivity and salinity surveys. SGD measurements using benthic chambers placed on the floor of the Flic-en-Flac Lagoon showed discharge rates up to 500 cm/day. Large variability in SGD was observed over distances of a few meters, which were attributed to different geomorphological features. Deployments of automated seepage meters captured the spatial and temporal variability of SGD with a mean seepage rate of 10 cm/day. The stable isotopic composition of submarine waters was characterized by significant variability and heavy isotope enrichment and was used to predict the contribution of fresh terrestrially derived groundwater to SGD (range from a few % to almost 100 %). The integrated SGD flux, estimated from seepage meters placed parallel to the shoreline, was 35 m3/m day, which was in a reasonable agreement with results obtained from hydrologic water balance calculation (26 m3/m day). SGD calculated from the radon inventory method using in situ radon measurements were between 5 and 56 m3/m per day. Low concentrations of radium isotopes observed in the lagoon water reflected the low abundance of U and Th in the basalt that makes up the island. High SGD rates contribute to high nutrients loading to the lagoon, potentially leading to eutrophication. Each of the applied methods yielded unique information about the character and magnitude of SGD. The results of the intercomparison studies have resulted a better understanding of groundwater-seawater interactions in coastal regions. Such information is an important pre-requisite for the protection management of coastal freshwater resources.The financial support provided by the IOC and IHP of UNESCO for travel arrangements, and by the IAEA’s Marine Environment Laboratories for logistics is highly acknowledged. MAC and MEG were supported in part by the US National Science Foundation (OCE-0425061 and OCE-0751525). PPP acknowledges a support provided by the EU Research & Development Operational Program funded by the ERDF (project No. 26240220004), and the Slovak Scientific Agency VEGA (grant No. 1/108/08). The International Atomic Energy Agency is grateful to the Government of the Principality of Monaco for support provided to its Marine Environment Laboratories