Dulaiova Henrieta

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  • Preprint
    Geochemical and physical sources of radon variation in a subterranean estuary — implications for groundwater radon activities in submarine groundwater discharge studies
    ( 2007-12-13) Dulaiova, Henrieta ; Gonneea, Meagan E. ; Henderson, Paul B. ; Charette, Matthew A.
    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.
  • Article
    GEOTRACES radium isotopes interlaboratory comparison experiment
    (Association for the Sciences of Limnology and Oceanography, 2012-06) Charette, Matthew A. ; Dulaiova, Henrieta ; Gonneea, Meagan E. ; Henderson, Paul B. ; Moore, Willard S. ; Scholten, Jan C. ; Pham, Mai Khanh
    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.
  • Preprint
    A new method for the determination of low-level actinium-227 in geological samples
    ( 2012-07-31) Dulaiova, Henrieta ; Sims, Kenneth W. W. ; Charette, Matthew A. ; Prytulak, Julie ; Blusztajn, Jerzy S.
    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.
  • Preprint
    Coupled radon, methane and nitrate sensors for large-scale assessment of groundwater discharge and non-point source pollution to coastal waters
    ( 2009-12-09) Dulaiova, Henrieta ; Camilli, Richard ; Henderson, Paul B. ; Charette, Matthew A.
    We constructed a survey system of radon/methane/nitrate/salinity to find sites of submarine groundwater discharge (SGD) and groundwater nitrate input. We deployed the system in Waquoit Bay and Boston Harbor, MA where we derived SGD rates using a mass balance of radon with methane serving as a fine resolution qualitative indicator of groundwater. In Waquoit Bay we identified several locations of enhanced groundwater discharge, out of which two (Childs and Quashnet Rivers) were studied in more detail. The Childs River was characterized by high nitrate input via groundwater discharge, while the Quashnet River SGD was notable but not a significant source of nitrate. Our radon survey of Boston Harbor revealed several sites with significant SGD, out of these Inner Harbor and parts of Dorchester Bay and Quincy Bay had groundwater fluxes accompanied by significant water column nitrogen concentrations. The survey system has proven effective in revealing areas of SGD and non-point source pollution.
  • Preprint
    Preparation of Mn-fiber standards for the efficiency calibration of the delayed coincidence counting system (RaDeCC)
    ( 2010-04) Scholten, Jan C. ; Pham, Mai Khanh ; Blinova, Oxana ; Charette, Matthew A. ; Dulaiova, Henrieta ; Eriksson, Mats
    Precise measurements of the short lived radium isotopes 223Ra and 224Ra by means of the delayed coincidence counting system (RaDeCC) rely on an efficiency calibration of this system using Mn-fiber standards for which radium activities are exactly known. We prepared seventeen different standards by placing Mn-fibers in seawater spiked with various amounts of 227Ac (with 223Ra in radioactive equilibrium), 228Th (in radioactive equilibrium with 232Th and 224Ra) and 226Ra. We tested for quantitative adsorption of 227Ac and 228Th on the Mn-fibers by: (1) measuring 227Ac and 232Th in the residual solutions after preparing the Mn-fiber standards and (2) monitoring their 223Ra and 224Ra activities over a period of ~100 days. In the residual solutions, the activities of 227Ac and 232Th were < 1.0 % and < 5.3 %, respectively, of the activities initially added to the Mn-fibers. Our results indicate that Milli-Q water washing of the Mn-fibers is the major source of our observed losses of thorium. Measurements of 227Ac standards over 1½ years indicate a significant decrease of measurable 223Ra with time prohibiting the long-term use of 227Ac Mn-fiber standards. We found the 224Ra efficiency to be independent of the range of 227Ac, 228Th and 226Ra activities on the Mn-fibers standards used. The efficiency determination for 223Ra, however, may be biased in the case of relatively high 224Ra activities due to insufficient correction of chance of coincidence. Thus we suggest using a single 227Ac Mn-fiber standard for the efficiency determination for 223Ra.
  • Preprint
    Evaluation of the flushing rates of Apalachicola Bay, Florida via natural geochemical tracers
    ( 2007-07-10) Dulaiova, Henrieta ; Burnett, William C.
    We used naturally occurring radium isotopes as tracers of water exchange in Apalachicola Bay, a shallow coastal-plain estuary in northwestern Florida. The bay receives fresh water and radium from the Apalachicola River, and mixes with Gulf of Mexico waters through four inlets. We deployed moored buoys with attached Mn-fibers at several stations throughout the estuary during two summer and two winter periods. After deployment for at least one tidal cycle we measured the ratio of the two short-lived radium isotopes 223Ra (half-life = 11 d) and 224Ra (3.6 d) to estimate “radium ages” of the water in the bay. During our four seasonal deployments the river discharge ranged from 338 to 1016 m3 s- 1. According to our calculations the water turnover time in the bay during these samplings ranged from 6 to 12 days. Age contours in the bay showed that winds and tides as well as river discharge influence the water movement and the residence time of freshwater in the bay. We also calculated the mean age of river water in the bay which was between 5 to 9 days during the studied periods. We suggest that this approach can be used to quantify transport processes of dissolved substances in the bay. For example, soluble nutrient or pollutant transport rates from a point source could be examined. We conclude that the radium age technique is well suited for flushing rate calculations in river dominated shallow estuaries.
  • Preprint
    Assessment of groundwater discharges into West Neck Bay, New York, via natural tracers
    ( 2006-05-21) Dulaiova, Henrieta ; Burnett, William C. ; Chanton, Jeffrey P. ; Moore, Willard S. ; Bokuniewicz, Henry J. ; Charette, Matthew A. ; Sholkovitz, Edward R.
    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.
  • Article
    Erratum : GEOTRACES radium isotopes interlaboratory comparison experiment
    (Association for the Sciences of Limnology and Oceanography, 2012-06) Charette, Matthew A. ; Dulaiova, Henrieta ; Gonneea, Meagan E. ; Henderson, Paul B. ; Moore, Willard S. ; Scholten, Jan C. ; Pham, Mai Khanh
    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.
  • Article
    Shelf-derived iron inputs drive biological productivity in the southern Drake Passage
    (American Geophysical Union, 2009-10-27) Dulaiova, Henrieta ; Ardelan, M. V. ; Henderson, Paul B. ; Charette, Matthew A.
    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.
  • Preprint
    New perspectives on radium behavior within a subterranean estuary
    ( 2007-04-02) Gonneea, Meagan E. ; Morris, Paul J. ; Dulaiova, Henrieta ; Charette, Matthew A.
    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.
  • Article
    Natural iron enrichment around the Antarctic Peninsula in the Southern Ocean
    (Copernicus Publications on behalf of the European Geosciences Union, 2010-01-05) Ardelan, M. V. ; Holm-Hansen, O. ; Hewes, C. D. ; Reiss, Christian S. ; Silva, N. S. ; Dulaiova, Henrieta ; Steinnes, E. ; Sakshaug, E.
    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.
  • Article
    Cesium-134 and 137 activities in the central North Pacific Ocean after the Fukushima Dai-ichi Nuclear Power Plant accident
    (Copernicus Publications on behalf of the European Geosciences Union, 2013-09-23) Kamenik, J. ; Dulaiova, Henrieta ; Buesseler, Ken O. ; Pike, Steven M. ; Stastna, K.
    Surface seawater 134Cs and 137Cs samples were collected in the central and western North Pacific Ocean during the 2 yr after the Fukushima Dai-ichi Nuclear Power Plant accident to monitor dispersion patterns of these radioisotopes towards the Hawaiian Islands. In the absence of other recent sources and due to its short half-life, only those parts of the Pacific Ocean would have detectable 134Cs values that were impacted by Fukushima releases. Between March and May 2011, 134Cs was not detected around the Hawaiian Islands and Guam. Here, most 137Cs activities (1.2–1.5 Bq m–3) were in the range of expected preexisting levels. Some samples north of the Hawaiian Islands (1.6–1.8 Bq m–3) were elevated above the 23-month baseline established in surface seawater in Hawaii indicating that those might carry atmospheric fallout. The 23-month time-series analysis of surface seawater from Hawaii did not reveal any seasonal variability or trends, with an average activity of 1.46 ± 0.06 Bq m–3 (Station Aloha, 18 values). In contrast, samples collected between Japan and Hawaii contained 134Cs activities in the range of 1–4 Bq m–3, and 137Cs levels were about 2–3 times above the preexisting activities. We found that the southern boundary of the Kuroshio and Kuroshio extension currents represented a boundary for radiation dispersion with higher activities detected within and north of the major currents. The radiation plume has not been detected over the past 2 yr at the main Hawaiian Islands due to the transport patterns across the Kuroshio and Kuroshio extension currents.