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M. Baskaran

Publications and source records attributed to M. Baskaran.

11 recordsLinked to original sources

Constraints on the utility of MnO 2 cartridge method for the extraction of radionuclides: A case study using 234 Th

[1] Large volume (10 2 -10 3 L) seawater samples are routinely processed to investigate the partitioning of particle reactive radionuclides and Ra between solution and size-fractionated suspended particulate matter. One of the most frequently used methods to preconcentrate these nuclides from such large volumes involves extraction onto three filter cartridges (a prefilter for particulate species and two MnO 2 -coated filters for dissolved species) connected in series. This method assumes that the extraction efficiency is uniform for both MnO 2 -coated cartridges, that no dissolved species are removed by the prefilter, and that any adsorbed radionuclides are not desorbed from the MnO 2 -coated cartridges during filtration. In this study, we utilized 234 Th-spiked coastal seawater and deionized water to address the removal of dissolved Th onto prefilters and MnO 2 -coated filter cartridges. Experimental results provide the first data that indicate (1) a small fraction of dissolved Th (<6%) can be removed by the prefilter cartridge; (2) a small fraction of dissolved Th (<5%) retained by the MnO 2 surface can also be desorbed, which undermines the assumption of uniform extraction efficiency for Th; and (3) the absolute and relative extraction efficiencies can vary widely. These experiments provide insight on the variability of the extraction efficiency of MnO 2 -coated filter cartridges by comparing the relative and absolute efficiencies and recommend the use of a constant efficiency on the combined activity from two filter cartridges connected in series for future studies of dissolved 234 Th and other radionuclides in natural waters using sequential filtration/extraction methods. ?? 2009 by the American Geophysical Union.

Geochemistry, Geophysics, Geosystems↗

Seasonal variations on the residence times and partitioning of short-lived radionuclides ( 234 Th, 7 Be and 210 Pb) and depositional fluxes of 7 Be and 210 Pb in Tampa Bay, Florida

Historically, Tampa Bay has been impacted heavily by a wide range of anthropogenic perturbations that may include, agricultural-, shipping-, phosphate mining/distribution-related activities, as well as a burgeoning coastal population. Due to the presence of U-rich underlying sediments, elevated activities of U- and Th-series daughter products may be naturally released into this system. This region is also known for summer thunderstorms and corresponding increases in precipitation and surface water runoff. Only limited work has been conducted on the partitioning of particle-reactive radionuclides (such as 7 Be, 210 Pb, and 234 Th) in such a dynamic coastal system. We investigated both the removal residence time and partitioning of these radionuclides between filter-retained particulate matter (≥ 0.5 μm) and the filtrate (< 0.5 μm) phase during late spring (June 2003) and mid summer (August 2003) in the water column of Tampa Bay. Our results indicate that the partitioning of 7 Be, 210 Pb, and 234 Th between filtrate and filter-retained phase is controlled foremost by enhanced bottom resuspension events during summer thunderstorms. As a consequence, no significant relationship exists between the distribution coefficients (Kd values) of these isotopes and the concentration of suspended particulate matter (SPM). Relatively faster recycling rates of atmospheric water vapor derived from the ocean results in lower atmospheric depositional fluxes of 210 Pb to the study site than predicted. The relationship between 7 Be and 210 Pb in bulk (wet + dry) deposition is compared to their respective water column activities. The residence times of particulate and dissolved 234 Th, 7 Be and 210 Pb, as well the distribution coefficients of these radionuclides, are then compared to values reported in other coastal systems.

Florida↗

Ra and Rn isotopes as natural tracers of submarine groundwater discharge in Tampa Bay, Florida

A suite of naturally occurring radionuclides in the U/Th decay series ( 222 Rn, 223,224,226,228 Ra) were studied during wet and dry conditions in Tampa Bay, Florida, to evaluate their utility as groundwater discharge tracers, both within the bay proper and within the Alafia River/estuary — a prominent free-flowing river that empties into the bay. In Tampa Bay, almost 30% of the combined riverine inputs still remain ungauged. Consequently, groundwater/surface water (hyporheic) exchange in the discharging coastal rivers, as well as submarine groundwater discharge (SGD) within the bay, are still unresolved components of this system's water and material budgets. Based on known inputs and sinks, there exists an excess of 226 Ra in the water column of Tampa Bay, which can be evaluated in terms of a submarine groundwater contribution to the bay proper. Submarine groundwater discharge rates calculated using a mass balance of excess 226 Ra ranged from 2.2 to 14.5 L m − 2 day − 1 , depending on whether the estuarine residence time was calculated using 224 Ra/xs 228 Ra isotope ratios, or whether a long term, averaged model-derived estuarine residence time was used. When extrapolated to the total shoreline length of the bay, such SGD rates ranged from 1.6 to 10.3 m 3 m − 1 day − 1 . Activities of 222 Rn were also elevated in surface water and shallow groundwater of the bay, as well as in the Alafia River estuary, where upstream activities as high as 250 dpm L − 1 indicate enhanced groundwater/surface water exchange, facilitated by an active spring vent. From average nutrient concentrations of 39 shallow, brackish, groundwater samples, rates of nutrient loading into Tampa Bay by SGD rates were estimated, and these ranged from 0.2 to 1.4 × 10 5 mol day − 1 (PO 4 3− ), 0.9–6.2 × 10 5 mol day − 1 (SiO 4 − ), 0.7–5.0 × 10 5 mol day − 1 (dissolved organic nitrogen, DON), and 0.2–1.4 × 10 6 mol day − 1 (total dissolved nitrogen, TDN). Such nutrient loading estimates, when compared to average river discharge estimates (e.g., TDN = 6.9 × 10 5 mol day − 1 ), suggest that SGD-derived nutrient fluxes to Tampa Bay are indeed important components to the overall nutrient economy of these coastal waters.

Florida↗

Biogeochemical transport in the Loxahatchee River estuary, Florida: The role of submarine groundwater discharge

The distributions of dissolved organic carbon (DOC), Ba, U, and a suite of naturally occurring radionuclides in the U/Th decay series (222Rn, 223,224,226,228Ra) were studied during high- and low-discharge conditions in the Loxahatchee River estuary, Florida to examine the role of submarine groundwater discharge in estuarine transport. The fresh water endmember of this still relatively pristine estuary may reflect not only river-borne constituents, but also those advected during active groundwater/surface water (hyporheic) exchange. During both discharge conditions, Ba concentrations indicated slight non-conservative mixing. Such Ba excesses could be attributed either to submarine groundwater discharge or particle desorption processes. Estuarine dissolved organic carbon concentrations were highest at salinities closest to zero. Uranium distributions were lowest in the fresh water sites and mixed mostly conservatively with an increase in salinity. Suspended particulate matter (SPM) concentrations were generally lowest (< 5??mg L- 1) close to zero salinity and increased several-fold (??? 18??mg L- 1; low discharge) toward the seaward endmember, which may be attributed to dynamic resuspension of bottom sediments within Jupiter Inlet. Surface water-column 222Rn activities were most elevated (> 28??dpm L- 1) at the freshwater endmember of the estuary and appear to identify regions of the river most influenced by the discharge of fresh groundwater. Activities of four naturally occurring isotopes of Ra (223,224,226,228Ra) in this estuary and select adjacent shallow groundwater wells yield mean estuarine water-mass transit times of less than 1 day; these values are in close agreement to those calculated by tidal prism and tidal frequency. Submarine groundwater discharge rates to the Loxahatchee River estuary were calculated using a tidal prism approach, an excess 226Ra mass balance, and an electromagnetic seepage meter. Average SGD rates ranged from 1.0 to 3.8 ?? 105??m3 d- 1 (20-74??L m- 2 d- 1), depending on river-discharge stage. Such calculated SGD estimates, which must include both a recirculated as well as fresh water component, are in close agreement with results obtained from a first-order watershed mass balance. Average submarine groundwater discharge rates yield NH4+ and PO4- 3 flux estimates to the Loxahatchee River estuary that range from 62.7 to 1063.1 and 69.2 to 378.5????mol m- 2 d- 1, respectively, depending on river stage. SGD-derived nutrient flux rates are compared to yearly computed riverine total N and total P load estimates. ?? 2006 Elsevier B.V. All rights reserved.

Marine Chemistry↗

Uranium distribution in the coastal waters and pore waters of Tampa Bay, Florida

The geochemical reactivity of uranium (238U) and dissolved organic carbon (DOC), Fe, Mn, Ba, and V was investigated in the water column, pore waters, and across a river/estuarine mixing zone in Tampa Bay, Florida. This large estuary is impacted both by diverse anthropogenic activity and by extensive U-rich phosphatic deposits. Thus, the estuarine behavior of uranium may be examined relative to such known U enrichments and anthropogenic perturbations. Dissolved (< 0.45??m) uranium exhibited both removal and enrichment processes across the Alafia River/estuarine mixing zone relative to conservative mixing. Such non-conservative U behavior may be attributed to: i) physical mixing processes within the river; ii) U carrier phase reactivity; and/or iii) fluid exchange processes across sediment/water interface. In the bay proper, U concentrations were ?????2 to 3 times greater than those reported for other estuarine systems and are likely a result of erosional inputs from the extensive, underlying U-rich phosphatic deposits. Whereas dissolved U concentrations generally did not approach seawater values (13.6??nM) along the Alafia River salinity transect, water column U concentrations exceeded 16??nM in select regions of the bay. Within the hydrogeological framework of the bay, such enriched U may also be derived from advective fluid transport processes across the sediment/water interface, such as submarine groundwater discharge (SGD) or hyporheic exchange within coastal rivers. Pore water profiles of U in Tampa Bay show both a flux into and out of bottom sediments, and average, diffusive U pore water fluxes (Jdiff) ranged from - 82.0 to 116.6??mol d- 1. It is likely that negative U fluxes imply seawater entrainment or infiltration (i.e., submarine groundwater recharge), which may contribute to the removal of water column uranium. For comparison, a bay-wide, Ra-derived submarine groundwater discharge estimate for Tampa Bay (8??L m- 2 d- 1) yielded an average, advective (JSGD) U flux of 112.9??mol d- 1. In Tampa Bay, the estuarine distribution of U indicates a strong natural, geologic control that may also be influenced by enhanced fluid transport processes across the sediment/water interface. ?? 2006 Elsevier B.V. All rights reserved.

Marine Chemistry↗

Historical trace element distribution in sediments from the Mississippi River delta

Five sediment cores were collected on the shelf of the inner Mississippi Bight in June 2003 for a suite of radionuclides to establish geochronologies and trace elements to examine patterns of contaminant deposition and accumulation. Core sites were chosen to reflect a matrix of variable water depths, proximity to the Mississippi River mouth as the primary source for terrigenous particles, and extent and duration of summertime water column hypoxia. The vertical distribution of 239,240Pu and 210Pbxs (= 210Pbtotal - 226Ra) provided reliable geochronological age constraints to develop models for mass accumulation rates and historic trace element inputs and variations. Mass accumulation rates ranged from 0.27 to 0.87 g cm-2 yr-1 and were internally consistent using either 210Pbxs or 239,240Pu. Measured inventories of 137Cs, 239,240Pu, and 210Pbxs were compared to atmospheric deposition rates to quantify potential sediment focusing or winnowing. Observed variability in calculated mass accumulation rates may be attributed foremost to site-specific proximity to the river mouth (i.e., sediment source), variability in water depth, and enhanced sediment focusing at the Mississippi River canyon site. Trace element concentrations were first normalized to Al, and then Al-normalized enrichment factors (ANEF) were calculated based on preanthropogenic and crustal trace element abundances. These ANEFs were typically > 1 for V and Ba, while for most other elements studied, either no enrichment or depletion was observed. The enrichment of Ba may be related, in part, to the seasonal occurrence of oxygen-depleted subsurface waters off the Mississippi River delta, as well as being an ubiquitous by-product of the petroleum industry. ?? 2006 Estuarine Research Federation.

Estuaries and Coasts↗

Is the extraction of thorium onto MnO 2 -coated filter cartridges uniform?

Large-volume (i.e., 10 2 - 10 3 L) seawater samples are traditionally required to study the partitioning of particle-reactive radionuclides between solution and size-fractionated particulate matter. One of the most frequently used methods to preconcentrate the short-lived isotopes of Th ( 234 Th and 228 Th) from such large volumes of water involves the effective extraction of Th onto two MnO 2 -coated polypropylene cartridges. Determination of dissolved Th activities assumes that the two MnO 2 -coated filter cartridges extract Th uniformly (same extraction efficiency), but this assumption has not been rigorously validated. Any variability in the extraction efficiency of the two cartridges connected in series will directly introduce an error in the determination of final dissolved Th activity. In this article, we evaluated the variability in the extraction efficiency of MnO 2 -coated filter cartridges that were prepared under varying conditions. Thorium-234-spiked seawater was filtered in series through a manifold consisting of six MnO 2 -coated cartridges. From the activities of 234 Th retained in each cartridge, the relative (calculated from the activities in two successive cartridges) and absolute (ratio of 234 Th activity retained to the activity entered) extraction efficiency for each of the cartridges was calculated. At a constant flow rate and constant KMnO 4 saturation, the absolute extraction efficiency varied by -40% (from 54.1 to 93.8%) within the first two filter cartridges, and over 50% (from 32.3 to 89.3%) on all six MnO 2 cartridges. Our results confirm that a uniform extraction efficiency using two filters connected in series is rarely achieved. Using the average extraction efficiency of all cartridges, we propose a new approach that assumes a constant extraction efficiency. This method will reduce the error introduced by the assumption of uniform extraction efficiency in the determination of dissolved Th activities.

Open-File Report↗

Role of colloidal material in the removal of 234Th in the Canada basin of the Arctic Ocean

The phase partitioning of 234Th between dissolved (< 10-kiloDalton, kD), colloidal (10 kD - 0.4 ??m), and particulate (???0.5 ??m) matter across a horizontal transect, from a coastal station to the deep Canada Basin, and a vertical profile in the deep Canada Basin of the western Arctic Ocean was investigated. Concentrations of suspended particulate matter (SPM), dissolved, colloidal and particulate organic carbon, particulate organic nitrogen and nutrients (silicate, phosphate and nitrate) were also measured to assess transport and scavenging processes. Total 234Th (colloidal + particulate + dissolved) indicated deficiencies relative to secular equilibrium with its parent, 238U in the upper 100 m, which suggests active scavenging of 234Th onto particle surfaces. In contrast, at depths > 200m, general equilibrium existed between total 234Th and 238U. The inventory of SPM and the specific activity of particulate 234Th in the Canada Basin was about an order of magnitude higher than the profile reported for the Alpha Ridge ice camp station. This higher concentration of SPM in the southwestern Canada Basin is likely derived from ice-rafted sedimentary particles. Inventories of nutrients, and dissolved organic carbon and nitrogen in the upper 100 m of the Canada Basin are comparable to the other estimates for the central Arctic Ocean. Comparison of the mass concentrations of colloidal and filter-retained particulate matter as well as the activity of 234Th in these phases indicates that only a very small component of the colloidal material is actively involved in Th scavenging. Lower values of the conditional partition coefficient between the colloidal and dissolved phase indicate that the Arctic colloids are less reactive than colloidal material from other regions. The conditional partition coefficient between the filter-retained and dissolved phases (Kf) is generally higher than that for other regions, which is attributed to the higher complexation capacity of glacio-marine sedimentary particles in these waters. The 234Th-derived export of POC for the shelf and deep Canada Basin ranges between 5.6 and 6.5 mmol m-2 d-1, and is in agreement with other estimates reported for the central Arctic Ocean and Beaufort Sea. ?? 2003 Elsevier Ltd. All rights reserved.

Deep-Sea Research Part I: Oceanographic Research P↗

Temporal variations of natural and anthropogenic radionuclides in sea otter skull tissue in the North Pacific Ocean

Marine mammals being among the top predators in the food web tend to accumulate organic and inorganic contaminants from the environment. The body burden of contaminants in these species could reflect their foods and thus contaminant levels could serve as proxies on the changes of ecosystem. A pilot study was carried out to investigate the possibility of radionuclide leakage at Amchitka using a suite of sea otter ( Enhydra lutris ) skulls collected near Amchitka nuclear test-sites before (1950s) and after the testing (1990s), and at Adak, another Aleutian Island, about 300 km from Amchitka, where the potential impact of radionuclide leakage from Amchitka is expected to be negligible. In addition, the naturally occurring and anthropogenic radionuclide content on the sea otter skull was also utilized to investigate if there was any significant ecosystem changes in the environment. Concentration of 210 Pb in sea otter bones collected during the 1950s was significantly higher than those collected in the 1990s. We propose that among the various factors that could cause this higher enrichment in 210 Pb, changes in the sea otter prey is the most likely one. Comparison of the 137 Cs, 90 Sr, 239,240 Pu concentrations appear not to be significantly higher in sea otter skulls collected in 1990s from Amchitka where the underground tests in 1965–71 than those from Adak, although significant differences were detected among different groups collected at various times.

Journal of Environmental Radioactivity↗

Sediment chronology in San Francisco Bay, California, defined by 210 Pb, 234 Th, 137 Cs, and 239,340 Pu

Sediment chronologies based on radioisotope depth profiles were developed at two sites in the San Francisco Bay estuary to provide a framework for interpreting historical trends in organic compound and metal contaminant inputs. At Richardson Bay near the estuary mouth, sediments are highly mixed by biological and/or physical processes. Excess penetration ranged from 2 to more than 10 cm at eight coring sites, yielding surface sediment mixing coefficients ranging from 12 to 170 cm 2 /year. At the site chosen for contaminant analyses, excess activity was essentially constant over the upper 25 cm of the core with an exponential decrease below to the supported activity between 70 and 90 cm. Both and penetrated to 57-cm depth and have broad subsurface maxima between 33 and 41 cm. The best fit of the excess profile to a steady state sediment accumulation and mixing model yielded an accumulation rate of 0.825 g/cm 2 /year (0.89 cm/year at sediment surface), surface mixing coefficient of 71 cm 2 /year, and 33-cm mixed zone with a half-Gaussian depth dependence parameter of 9 cm. Simulations of and profiles using these parameters successfully predicted the maximum depth of penetration and the depth of maximum and activity. Profiles of successive 1-year hypothetical contaminant pulses were generated using this parameter set to determine the age distribution of sediments at any depth horizon. Because of mixing, sediment particles with a wide range of deposition dates occur at each depth. A sediment chronology was derived from this age distribution to assign the minimum age of deposition and a date of maximum deposition to a depth horizon. The minimum age of sediments in a given horizon is used to estimate the date of first appearance of a contaminant from its maximum depth of penetration. The date of maximum deposition is used to estimate the peak year of input for a contaminant from the depth interval with the highest concentration of that contaminant. Because of the extensive mixing, sediment-bound constituents are rapidly diluted with older material after deposition. In addition, contaminants persist in the mixed zone for many years after deposition. More than 75 years are required to bury 90% of a deposited contaminant below the mixed zone. Reconstructing contaminant inputs is limited to changes occurring on a 20-year time scale. In contrast, mixing is much lower relative to accumulation at a site in San Pablo Bay. Instead, periods of rapid deposition and/or erosion occurred as indicated by frequent sand-silt laminae in the X-radiograph. , , and excess activity all penetrated to about 120 cm. The distinct maxima in the fallout radionuclides at 105&ndash;110 cm yielded overall linear sedimentation rates of 3.9 to 4.1 cm/year, which are comparable to a rate of 4.5&plusmn;1.5 cm/year derived from the excess profile.

California↗

Constraints on the sedimentation history of San Francisco Bay from 14C and 10Be

Industrialization and urbanization around San Francisco Bay as well as mining and agriculture in the watersheds of the Sacramento and San Joaquin rivers have profoundly modified sedimentation patterns throughout the estuary. We provide some constraints on the onset of these erosional disturbances with 10Be data for three sediment cores: two from Richardson Bay, a small embayment near the mouth of San Francisco Bay, and one from San Pablo Bay, mid-way between the river delta and the mouth. Comparison of pre-disturbance sediment accumulation determined from three 14C-dated mollusk shells in one Richardson Bay core with more recent conditions determined from the distribution of 210Pb and 234Th [Fuller, C.C., van Geen, A., Baskaran, M, Anima, R.J., 1999. Sediment chronology in San Francisco Bay, California, defined by 210Pb, 234Th, 239,240Pu.] shows that the accumulation rate increased by an order of magnitude at this particular site. All three cores from San Francisco Bay show subsurface maxima in 10Be concentrations ranging in magnitude from 170 to 520 x 106 atoms/g. The transient nature of the increased 10Be input suggests that deforestation and agricultural develop- ment caused basin-wide erosion of surface soils enriched in 10Be. probably before the turn of the century.

California↗