David F. Reid

Radium, thorium, and actinium extraction from seawater using an improved manganese-oxide-coated fiber

Laboratory experiments were conducted to determine the efficiency with which improved manganese-oxide-coated acrylic fibers extract radium, thorium, and actinium from seawater. Tests were made using surface seawater spiked with227Ac,227Th, and223Ra. For sample volumes of approximately 30 liters and flow rates up to 0.5 liters per minute, radium and actinium are removed quantitatively. Approximately 80–95% of the thorium is removed under these same conditions.

Temporal variation of228Ra in the near-surface Gulf of Mexico

Abstract The Mn-fiber technique for extracting radium from seawater has proved useful for studying the marine geochemistry of 228 Ra. In the Gulf of Mexico, this technique was used to measure the surface and near-surface distribution of 226 Ra and 228 Ra. The observed surface distribution of 228 Ra, and particularly the radium activity ratio (228/226) can be explained by known circulation patterns, or, when local surface currents are not well understood, may provide insight into their general characteristics. The radium activity ratio has increased from 0.5 in 1968 to 0.7 in 1973 in the surface Gulf of Mexico. This observed increase cannot be attributed to known anthropogenic or natural source perturbations within the Caribbean Sea-Gulf of Mexico system. Possible causes include a change in the residence time for near-surface water, or variations in the relative dominance of the two sources for water entering the eastern Caribbean; the North Equatorial Current and the Guiana Current. The temporal distribution of 228 Ra is unstable and naturally variable over a time period less than or equal to five years in the Gulf of Mexico and by extrapolation, the Caribbean Sea. Therefore, its usefulness in calculations of eddy diffusion coefficients for these regions is greatly diminished.

Revised Lake Erie Postglacial Lake Level History Based on New Detailed Bathymetry

Abstract Holocene lake level history and paleogeography of Lake Erie are re-interpreted with the aid of new bathymetry, existing water budget data, and published information. Morphology and elevation of present and former shoreline features (sand ridges, forelands, spits, bars, and fans) record the water level at which they were formed. Of eighteen such features observed in Lake Erie, six occur nearshore and were formed at or near present lake level, and twelve features apparently formed at lower lake levels. It seems likely that lake level fell below the level of the outlet sill during the 9–6 ka climate optimum, when warmer and drier conditions prevailed. During such times lake level likely rose and fell as controlled by the water budget, within a window of constraint imposed by increases and decreases in evaporation, which would have varied directly with lake surface area. Near Buffalo, possible shoreline features occurring 3–6 km offshore at depths of 9–12 m could have formed at lower lake levels. Annual water volumes in each term of the water budget, (runoff, precipitation, and evaporation) are large relative to the volumetric capacity of Lake Erie itself. Such events as introduction of even a modest amount of upper Great Lakes water, or the onset of cooler and less dry climate conditions, could cause significant, rapid, lake level rise. Schematic reconstructions illustrate changing paleogeography and a Holocene lake level history which has varied with: blocking/ unblocking of outlet sills; erosion of outlet sills; distance from outlet sills; differential isostatic rebound; upper Great Lakes drainage flowing into or bypassing the lake; and climate-driven water budget of the Lake Erie drainage basin.

EFFECTS OF PROPOSED PHYSICAL BALLAST TANK TREATMENTS ON AQUATIC INVERTEBRATE RESTING EGGS

Adaptations in aquatic invertebrate resting eggs that confer protection from natural catastrophic events also could confer protection from treatments applied to ballast water for biological invasion vector management. To evaluate the potential efficacy of physical ballast water treatment methods, the present study examined the acute toxicity of heat (flash and holding methods), ultraviolet (UV) radiation (254 nm), and deoxygenation (acute and chronic) on resting eggs of the freshwater cladoceran Daphnia mendotae and the marine brine shrimp Artemia sp. Both D. mendotae and Artemia sp. were similarly sensitive to flash exposures of heat (100% mortality at 70 degrees C), but D. mendotae were much more sensitive to prolonged exposures. Exposure to 4,000 mJ/cm2 of UV radiation resulted in mortality rates of 59% in Artemia sp. and 91% in D. mendotae. Deoxygenation to an oxygen concentration of 1 mg/L was maximally toxic to both species. Deoxygenation suppressed hatching of D. mendotae resting eggs at oxygen concentrations of less than 5.5 mg/L and of Artemia sp. resting eggs at concentrations of less than 1 mg/L. Results suggest that UV radiation and deoxygenation are not viable treatment methods with respect to invertebrate resting eggs because of the impracticality of producing sufficient UV doses and the suppression of hatching at low oxygen concentrations. Results also suggest that the treatment temperatures required to kill resting eggs are much higher than those reported to be effective against other invertebrate life stages and species. The results, however, do not preclude the effectiveness of these treatments against other organisms or life stages. Nevertheless, if ballast tank treatment systems employing the tested methods are intended to include mitigation of viable resting eggs, then physical removal of large resting eggs and ephippia via filtration would be a necessary initial step.

Sensitivity of aquatic invertebrate resting eggs to SeaKleen® (Menadione): A test of potential ballast tank treatment options

The introduction of aquatic species in resting life stages by the release of ballast water is a less well-known but potentially important invasive species vector. Best-management practices designed to minimize transport of ballast water cannot eliminate this threat, because residual water and sediment are retained in ballast tanks after draining. To evaluate the potential efficacy of chemical treatment of residual material in ship ballast tanks, the present study examined the acute toxicity of the proposed biocide SeaKleen (menadione; Garnett, Watkinsville, GA, USA) on resting eggs of Brachionus plicatilis (a marine rotifer), a freshwater copepod, Daphnia mendotae (a freshwater cladoceran), and Artemia sp. (a marine brine shrimp). SeaKleen was toxic to resting eggs of all taxa. Daphnia mendotae resting eggs encased in protective ephippia were the least sensitive, as indicated by a 24-h lethal concentration of toxicant to 90% of organisms of 8.7 mg/L (95% confidence interval, +/- 0.1 mg/L). SeaKleen induced teratogenic effects in D. mendotae and Artemia sp. Exposure to sunlight quickly degraded SeaKleen, which lost all toxicity after 72 h outdoors. SeaKleen increased in toxicity slightly after 72 h in darkness. Burial of D. mendotae ephippia in natural lake sediment reduced SeaKleen toxicity by a factor of 20. Reduced toxicity in the presence of sediment raises serious doubts as to the potential for this, or any, chemical biocide to kill aquatic invertebrate resting stages buried in sediment retained in ship ballast tanks.

Aquatic invertebrate resting egg sensitivity to glutaraldehyde and sodium hypochlorite

Ballast tank treatment technologies are currently in development to reduce the risk of acquiring or transporting viable aquatic organisms that could be introduced to ecosystems and become invasive. Aquatic invertebrate resting eggs represent a challenge to such technologies because of morphological and biochemical adaptations to stress that also protect eggs from artificial stressors. To evaluate the potential efficacy of chemical biocides for ballast tank treatment, the present study examined the acute toxicity of glutaraldehyde and sodium hypochlorite on resting eggs of the freshwater cladoceran Daphnia mendotae and marine brine shrimp (Artemia sp.). Glutaraldehyde was toxic to resting eggs of Artemia sp., as indicated by a lethal concentration to 90% of organisms (LC90) of 95% confidence interval (226 +/- 10 mg/L). Daphnia mendotae, in contrast, displayed erratic responses to glutaraldehyde. Sodium hypochlorite was similarly toxic to resting eggs of Artemia sp. and D. mendotae, which displayed LC90s of 86.5 +/- 3.0 and 78.3 +/- 1.6 mg/L, respectively. Burial in sediment protected resting eggs from toxicants. The present results corroborate those from previous investigations of resting egg sensitivity to artificial stressors, supporting the conclusions that resting eggs are less sensitive than other life stages to artificial stressors and that chemical biocide concentrations effective against other life stages may be ineffective against resting stages.

Concentrated sodium chloride brine solutions as an additional treatment for preventing the introduction of nonindigenous species in the ballast tanks of ships declaring no ballast on board

Currently, seawater flushing is the only management strategy for reducing the number of viable organisms in residual sediments and water of ballast tanks of vessels declaring no ballast on board (NOBOB) that traffic ports of the eastern United States. Previously, we identified several species of freshwater and brackish-water peracarid crustaceans able to survive the osmotic shock that occurs during open-ocean ballast water exchange and, potentially, to disperse over long distances via ballasted ships and NOBOB vessels. We tested the efficacy of concentrated sodium chloride brine solutions as an additional treatment for eradicating the halotolerant taxa often present in the ballast tanks of NOBOB ships. The lowest brine treatments (30 ppt for 1 h) caused 100% mortality in several species of cladocerans and copepods collected from oligohaline habitats. Several brackish-water peracarid crustaceans, however, including some that can survive in freshwater as well, required higher brine concentrations and longer exposure durations (45-60 ppt for 3-24 h). The most resilient animals were widely introduced peracarid crustaceans that generally prefer mesohaline habitats but do not tolerate freshwater (required brine treatments of 60-110 ppt for 3-24 h). Brine treatments (30 ppt) also required less time to cause 100% mortality for eight taxa compared with treatments using 34 ppt seawater. Based on these experiments and published data, we present treatment strategies for the ballast tank biota often associated with NOBOB vessels entering the Great Lakes region. We estimate the lethal dosage of brine for 95% of the species in our experiments to be 110 ppt (95% confidence interval, 85-192 ppt) when the exposure time is 1 h and 60 ppt (95% confidence interval, 48-98 ppt) when the exposure duration is 6 h or longer.

Radium in the near-surface Caribbean Sea

Abstract Recent radium measurements from the near-surface Caribbean Sea are presented. The surface horizontal and vertical distributions of 226 Ra are essentially the same as reported by Szabo et al. (1967) for the early 1960s. The 226 Ra activity at the surface is relatively uniform across the Caribbean, with an average of 8.2±0.4dpm/100kg . The subsurface distribution to ∼200 m averages 7.8±0.4dpm/100kg and increases slowly below 200 m. reaching ∼9.5 dpm/100 kg at 560 m. In contrast to 226 Ra, the surface concentration of 228 Ra was much more variable in both time and space. An average increase of 33% was found between 1968 and 1976 in the western Caribbean and during both years an anomalously high 228 Ra activity was found in the eastern Caribbean. These data support previous hypotheses that water entering the eastern Caribbean has been enriched in 228 Ra prior to entry and that variable mixing of the Atlantic water masses found to the northeast and southeast of the Lesser Antilles may produce temporal variations in the near-surface 228 Ra activity. Scatter plots of 228 Ra vs. salinity and sigma-t indicate that the near-surface vertical distribution of 228 Ra in the Caribbean Sea is predominantly influenced by advection. Thus 228 Ra cannot be used to study near-surface vertical mixing rates in this region.

Small Rimmed Depression in Lake Ontario: An Impact Crater?

Abstract Detailed bathymetry of Lake Ontario reveals a small circular feature and adjoining SWtrending ridge associated with a small topographic high identified as Charity Shoal on nautical charts. The feature consists of a circular basin 1,000 m in diameter and 19+ m deep, completely surrounded by a low-relief rim that rises to within 5 m of the water surface over much of its extent. A N53E tapering ridge is contiguous with the feature and extends southwestward. Bedrock consists of middle Ordovician limestones 100-150 m thick overlying rocks of Precambrian age. The limited information available suggests that the feature may be an extraterrestrial impact crater, but other origins such as sinkhole, volcanic cone, or kettle, are not ruled out. Time of formation is not known, but likely times include the Pleistocene when the area was exposed by glacial erosion, the middle Ordovician near the time of deposition of limestones, or the Cambro-Ordovician or Precambrian when erosion surfaces of this age were exposed. A subtle negative magnetic anomaly coincides with the feature and is consistent with an impact origin, though not positively diagnostic. Relief of the feature is low compared to that typical of an impact crater of this size. Glaciation may have diminished relief by eroding the rim and filling the central basin with drift. Verification as an impact crater will require detailed geophysical surveys and collection and analyses of samples from in and around the structure.