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An evaluation of uranium-series dating of fossil echinoids from southern California Pleistocene marine terraces

Fossil sea urchins ( Strongylocentrotus ) from Pleistocene marine terraces on the southern California Channel Islands have been dated by the uranium-series method in order to test the suitability of echinoids for dating marine terraces. Results indicate that urchin plates and spines do not behave as closed systems with respect to both uranium and thorium. Calculated ages based on these data do not agree with uranium-series ages (120,000 and 127,000 yrs) obtained previously from corals from the same localities. Thus, fossil sea urchins ( Strongylocentrotus ) are not considered suitable for uranium-series dating of Pleistocene marine terrace deposits.

California

Intrinsic germanium detector used in borehole sonde for uranium exploration

A borehole sonde (~1.7 m long; 7.3 cm diameter) using a 200 mm 2 planar intrinsic germanium detector, mounted in a cryostat cooled by removable canisters of frozen propane, has been constructed and tested. The sonde is especially useful in measuring X- and low-energy gamma-ray spectra (40–400 keV). Laboratory tests in an artificial borehole facility indicate its potential for in-situ uranium analyses in boreholes irrespective of the state of equilibrium in the uranium series. Both natural gamma-ray and neutron-activation gamma-ray spectra have been measured with the sonde. Although the neutron-activation technique yields greater sensitivity, improvements being made in the resolution and efficiency of intrinsic germanium detectors suggest that it will soon be possible to use a similar sonde in the passive mode for measurement of uranium in a borehole down to about 0.1% with acceptable accuracy. Using a similar detector and neutron activation, the sonde can be used to measure uranium down to 0.01%.

Nuclear Instruments and Methods

Organic tissues, graphite, and hydrocarbons in host rocks of the Rum Jungle Uranium Field, northern Australia

The Rum Jungle Uranium field consists of at least six early Proterozoic deposits that have been mined either for uranium and/or the associated base and precious metals. Organic matter in the host rocks of the Whites Formation and Coomalie Dolomite is now predominantly graphite, consistent with the metamorphic history of these rocks. For nine samples, the mean total organic carbon content is high (3.9 wt%) and ranged from 0.33 to 10.44 wt%. Palynological extracts from the host rocks include black, filamentous, stellate ( Eoastrion -like), and spherical morphotypes, which are typical of early Proterozoic microbiota. The colour, abundance, and shapes of these morphotypes reflect the thermal history, organic richness, and probable lacustrine biofacies of the host rocks. Routine analysis of rock thin sections and of palynological residues shows that mineral grains in some of the host rocks are coated with graphitized organic matter. The grain coating is presumed to result from ultimate thermal degradation of a petroleum phase that existed prior to metamorphism. Hydrocarbons are, however, still present in fluid inclusions within carbonates of the Coomalie Dolomite and lower Whites Formation. The fluid inclusions fluoresce dull orange in blue-light excitation and their hydrocarbon content is confirmed by gas chromatography of whole-rock extracts. Preliminary analysis of the oil suggests that it is migrated, and because it has escaped graphitization through metamorphism it is probably not of early Proterozoic age. The presence of live oil is consistent with fluid inclusion data that suggest subsequent, low-temperature brine migration through the rocks. The present observations support earlier suggestions that organic matter in the host formations trapped uranium to form protore. Subsequent fluid migrations probably brought additional uranium and other metals to these formations, and the organic matter provided a reducing environment for entrapment.

Rum Jungle Uranium Field, northern Australia

Uranium in big sagebrush from western U.S. and evidence of possible mineralization in the Owyhee mountains of Idaho

Two regional studies of big sagebrush ( Artemisia tridentata ), a widely distributed and dominant shrub in the western United States, have shown its responsiveness to known uranium mineralization in the Monument Hill and Pumpkin Buttes districts of the southern Powder River Basin, Wyoming, and the Uravan mineral belt area in southeastern Utah and southwestern Colorado. Uranium concentrations in the ash of 154 stem-and-leaf samples of sagebrush are plotted on two maps, one representing the sampling design for the Powder River Basin study, and the other representing the sampling design for the Colorado Plateaus, the Basin and Range, and the Columbia Plateaus physiographic provinces of the West. Sites having high concentrations in sagebrush correspond not only to the above uranium districts, but also reveal an area along the northeast flanks of the Owyhee Mountains in Idaho that should be further explored for its possible uranium potential.

Journal of Geochemical Exploration

Simulated fissioning of uranium and testing of the fission-track dating method

A computer program (FTD-SIM) faithfully simulates the fissioning of 238U with time and 235U with neutron dose. The simulation is based on first principles of physics where the fissioning of 238U with the flux of time is described by Ns = ??f 238Ut and the fissioning of 235U with the fluence of neutrons is described by Ni = ??235U??. The Poisson law is used to set the stochastic variation of fissioning within the uranium population. The life history of a given crystal can thus be traced under an infinite variety of age and irradiation conditions. A single dating attempt or up to 500 dating attempts on a given crystal population can be simulated by specifying the age of the crystal population, the size and variation in the areas to be counted, the amount and distribution of uranium, the neutron dose to be used and its variation, and the desired ratio of 238U to 235U. A variety of probability distributions can be applied to uranium and counting-area. The Price and Walker age equation is used to estimate age. The output of FTD-SIM includes the tabulated results of each individual dating attempt (sample) on demand and/or the summary statistics and histograms for multiple dating attempts (samples) including the sampling age. An analysis of the results from FTD-SIM shows that: (1) The external detector method is intrinsically more precise than the population method. (2) For the external detector method a correlation between spontaneous track count, Ns, and induced track count, Ni, results when the population of grains has a stochastic uranium content and/or when the counting areas between grains are stochastic. For the population method no correlation can exist. (3) In the external detector method the sampling distribution of age is independent of the number of grains counted. In the population method the sampling distribution of age is highly dependent on the number of grains counted. (4) Grains with zero-track counts, either in Ns or Ni, are in integral part of fissioning theory and under certain circumstances must be included in any estimate of age. (5) In estimating standard error of age the standard error of Ns and Ni and ?? must be accurately estimated and propagated through the age equation. Several statistical models are presently available to do so. ?? 1985.

Nuclear Tracks and Radiation Measurements (1982)

Uranium delivery and uptake in a montane wetland, north-central Colorado, USA

Comprehensive sampling of peat, underlying lakebed sediments, and coexisting waters of a naturally uraniferous montane wetland are combined with hydrologic measurements to define the important controls on uranium (U) supply and uptake. The major source of U to the wetland is groundwater flowing through locally fractured and faulted granite gneiss of Proterozoic age. Dissolved U concentrations in four springs and one seep ranged from 20 to 83 ppb (μg/l). Maximum U concentrations are ∼300 ppm (mg/kg) in lakebed sediments and >3000 ppm in peat. Uranium in lakebed sediments is primarily stratabound in the more organic-rich layers, but samples of similar organic content display variable U concentrations. Post-depositional modifications include variable additions of U delivered by groundwater. Uranium distribution in peat is heterogeneous and primarily controlled by proximity to groundwater-fed springs and seeps that act as local point sources of U, and by proximity to groundwater directed along the peat/lakebeds contact. Uranium is initially sorbed on various organic components of peat as oxidized U(VI) present in groundwater. Selective extractions indicate that the majority of sorbed U remains as the oxidized species despite reducing conditions that should favor formation of U(IV). Possible explanations are kinetic hindrances related to strong complex formation between uranyl and humic substances, inhibition of anaerobic bacterial activity by low supply of dissolved iron and sulfate, and by cold temperatures.

Colorado

Combining particle-tracking and geochemical data to assess public supply well vulnerability to arsenic and uranium

Flow-model particle-tracking results and geochemical data from seven study areas across the United States were analyzed using three statistical methods to test the hypothesis that these variables can successfully be used to assess public supply well vulnerability to arsenic and uranium. Principal components analysis indicated that arsenic and uranium concentrations were associated with particle-tracking variables that simulate time of travel and water fluxes through aquifer systems and also through specific redox and pH zones within aquifers. Time-of-travel variables are important because many geochemical reactions are kinetically limited, and geochemical zonation can account for different modes of mobilization and fate. Spearman correlation analysis established statistical significance for correlations of arsenic and uranium concentrations with variables derived using the particle-tracking routines. Correlations between uranium concentrations and particle-tracking variables were generally strongest for variables computed for distinct redox zones. Classification tree analysis on arsenic concentrations yielded a quantitative categorical model using time-of-travel variables and solid-phase-arsenic concentrations. The classification tree model accuracy on the learning data subset was 70%, and on the testing data subset, 79%, demonstrating one application in which particle-tracking variables can be used predictively in a quantitative screening-level assessment of public supply well vulnerability. Ground-water management actions that are based on avoidance of young ground water, reflecting the premise that young ground water is more vulnerable to anthropogenic contaminants than is old ground water, may inadvertently lead to increased vulnerability to natural contaminants due to the tendency for concentrations of many natural contaminants to increase with increasing ground-water residence time.

Journal of Hydrology

Volumetric determination of uranium: Titanous sulfate as reductant before oxidimetric titration

Need for a more rapid volumetric method for the routine determination of uranium in uranium-rich materials has led to the development of a method that uses titanous sulfate as a reductant before oxidimetric titration. Separation of the hydrogen sulfide group is not necessary. Interfering elements precipitated by cupferron are removed by automatic filtrations made simultaneously rather than by the longer chloroform extraction method. Uranium is reduced from VI to IV by addition of an excess of titanous sulfate solution, cupric ion serving as an indicator by forming red metallic copper when reduction is complete. The copper is reoxidized by addition of mercuric perchlorate. The reduced uranium is then determined by addition of excess ferric sulfate and titration with ceric sulfate. The method has proved to be rapid, accurate, and economical.

Analytical Chemistry

Using age tracers and decadal sampling to discern trends in nitrate, arsenic and uranium in groundwater beneath irrigated cropland

Repeat sampling and age tracers were used to examine trends in nitrate, arsenic and uranium concentrations in groundwater beneath irrigated cropland. Much higher nitrate concentrations in shallow modern groundwater were observed at both the Columbia Plateau and High Plains sites (median values of 10.2 and 15.4 mg/L as N, respectively) than in groundwater that recharged prior to the onset of intensive irrigation (median values of <1 and <4 mg/L as N, respectively). Repeat sampling of these well networks indicates that high nitrate concentrations in modern, shallow groundwater have been sustained for decades, posing a future risk to older, deeper groundwater used for drinking water. In fact, nitrate concentrations in older modern water (30-60 years since recharge) at the High Plains site have increased in the last decade. Groundwater irrigated areas in the Columbia Plateau tend to have higher nitrate concentrations than surface-water irrigated areas suggesting that repeated dissolution of land applied fertilizer during recirculation may be an important factor causing high nitrate concentrations in groundwater. Mobilization of uranium and arsenic by land surface activities is suggested by the higher concentrations of these constituents in modern, shallow groundwater than in older, deeper groundwater at the Columbia Plateau site. Bicarbonate concentrations in modern groundwater are positively correlated with uranium (r=0.72, p<0.01), suggesting bicarbonate may mobilize uranium in this system. A positive correlation between arsenic and phosphorus concentrations in modern groundwater (r=0.55, p<0.01) suggests that phosphate from fertilizer outcompetes arsenate for sorption sites, mobilizing sorbed arsenic derived from past pesticide use or other sources.

Environmental Science and Technology

Biogenic non-crystalline U(IV) revealed as major component in uranium ore deposits

Historically, it is believed that crystalline uraninite, produced via the abiotic reduction of hexavalent uranium (U (VI) ) is the dominant reduced U species formed in low-temperature uranium roll-front ore deposits. Here we show that non-crystalline U (IV) generated through biologically mediated U (VI) reduction is the predominant U (IV) species in an undisturbed U roll-front ore deposit in Wyoming, USA. Characterization of U species revealed that the majority ( ∼ 58-89%) of U is bound as U (IV) to C-containing organic functional groups or inorganic carbonate, while uraninite and U (VI) represent only minor components. The uranium deposit exhibited mostly 238 U-enriched isotope signatures, consistent with largely biotic reduction of U (VI) to U (IV) . This finding implies that biogenic processes are more important to uranium ore genesis than previously understood. The predominance of a relatively labile form of U (IV) also provides an opportunity for a more economical and environmentally benign mining process, as well as the design of more effective post-mining restoration strategies and human health-risk assessment.

Nature Communications

Isotopic composition and distribution of lead, uranium, and thorium in a Precambrian granite

The isotopic compositions and concentrations of lead and uranium have been determined in some separated minerals and the composite of a granite from Monmouth township, Haliburton County, Ontario. The chemical and mass spectrometric methods that were used are described. The age of the zircon from the granite is 1050 million years. Much of the lead, uranium, and thorium exists in chemically unstable and presumably interstitial phases of the granite. A comparison of the observed amounts of uranium, thorium, and lead in the various minerals with those amounts that should have been present, had these three elements existed within the minerals as closed systems, shows a non-balance of these elements in every case. It appears that the granite as a whole has closely approximated a closed system since it was formed with respect to uranium and its decay products, but has been an open system with respect to thorium and its decay products. Interpretations concerning the relationship of these data to lead ores are discussed.

GSA Bulletin

Iron-titanium oxide minerals and magnetic susceptibility anomalies in the Mariano Lake-Lake Valley cores-Constraints on conditions of uranium mineralization in the Morrison Formation, San Juan Basin, New Mexico

Petrographic study of the Mariano Lake-Lake Valley cores reveals three distinct zones of postdepositional alteration of detrital Fe-Ti (iron-titanium) oxide minerals in the Westwater Canyon Member of the Upper Jurassic Morrison Formation. In the uranium-bearing and adjacent portions of the Westwater Canyon, these detrital Fe-Ti oxide minerals have been thoroughly altered by leaching of iron. Stratigraphically lower parts of the Westwater Canyon and the underlying Recapture Member are characterized by preservation of Fe-Ti oxide grains, primarily magnetite and ilmenite, and of hematite, and by an absence of uranium concentrations. Partly destroyed Fe-Ti oxide minerals occupy an interval between the zones of destruction and preservation. Alteration patterns of the Fe-Ti oxide minerals are reflected in bore-hole magnetic susceptibility logs. Magnetic susceptibility response in the upper parts of the Westwater Canyon Member is flat and uniformly < 500 /xSI units, but at greater depths it fluctuates sharply, from <1,000 to nearly 8,000 μSI units. The boundary between uniformly low and high magnetic susceptibility response corresponds closely to the interval that divides the zone of completely altered from the zone of preserved detrital Fe-Ti oxide minerals. The alteration pattern suggests that solutions responsible for destruction of the Fe-Ti oxide minerals originated in the overlying Brushy Basin Member of the Morrison Formation. Previous studies indicate that these solutions were rich in soluble organic matter and perhaps in uranium. Uranium precipitation may have been controlled by a vertically fluctuating interface between organic-rich solutions and geochemically different fluids in which the detrital Fe-Ti oxide minerals were preserved.

New Mexico

Uranium deposits of the northern part of the Boulder Batholith, Montana

Uranium minerals and radioactivity anomalies occur in many silverlead veins and chalcedony veins and vein zones in the Boulder batholith of southwestern Montana. Pitchblende has been identified in a few silverlead veins. These silver-lead veins occupy shear zones along which there is no evidence of large-scale lateral displacement. The wall rock adjacent to the veins is intensely silicified and sericitized quartz monzonite and granodiorite. The veins have yielded substantial quantities of lead, silver, zinc, and gold. The silver-lead veins consist principally of galena, sphalerite, tetrahedrite, chalcopyrite, and pyrite in a gangue of light- to dark-gray quartz, altered rock, gouge, and subordinate chalcedony and carbonate minerals. No anomalous radioactivity nor uranium minerals have been found in similar veins in prebatholithic rocks of the area.Chalcedony veins and vein zones, some of which are uraniferous, are distinctly different from the silver-lead veins and, with a single exception, are known only in the batholith. The chalcedony vein zones consist of one or more discontinuous stringers or veins of chalcedony and microcrystalline quartz in silicified and sericitized quartz monzonite and granodiorite, and in less strongly altered alaskite. Only small amounts of silver ore have been produced from these chalcedony veins and vein zones. All of the veins are early Tertiary in age, but the silver-lead veins probably are older than the chalcedony veins. Uranium is closely associated with chalcedony and microcrystalline quartz in both types of veins. This association suggests that all of the uranium in the area is of the same age. If so, some of the silver-lead veins must have been re-opened during the period of chalcedony vein formation.

Montana

Diffusion features of uranium-vanadium deposits in Montezuma Canyon, Utah

Uranium-vanadium deposits in the Salt Wash Member of the Morrison Formation in Montezuma Canyon , San Juan County, Utah , exhibit zoning that is interpreted as a result of metal transport by diffusion . The concentric zones consist of a brown nonmineralized core, an olive-gray mineralized shell, and a gray nonmineralized outer zone. The brown zone is iron-stained, porous sandstone commonly containing abundant carbonaceous material. The curved mineralized layer completely encloses the brown zone, and is composed of oxidized uranium-vanadium minerals that impregnate sandstone. The gray zone is light-gray sandstone tightly cemented with calcite and commonly freckled with limonitic specks.Formation of the deposits most likely took place during Late Cretaceous or early Tertiary time when the ore-bearing sandstones were deeply buried and saturated with connate waters. The concentration of organic material in the brown zone suggests that this zone was once saturated with a reducing solution containing soluble organic compounds like alcohols and aldehydes derived from the organic material. The gray zone, on the other hand, was probably saturated with an oxidizing solution containing uranium and vanadium. Where these two solutions were in contact, oxidation-reduction reactions took place that caused the precipitation of low-valent uranium and vanadium minerals.The ellipsoidal shape of the ore layer and the lack of any exit or entrance for flowing solutions indicates that the dissolved metals moved through the gray zone by diffusion and were precipitated at the periphery of the reducing zone. Recent weathering and oxidation have altered the primary low-valent minerals to high-valent forms without noticeable leaching of the ore metals.

Utah

U-Pb isotope systematics and age of uranium mineralization, Midnite mine, Washington.

Uranium ores at the Midnite mine, near Spokane, Washington, occur in phyllites and calcsilicates of the Proterozoic Togo Formation, near the margins of an anomalously uraniferous, porphyritic quartz monzonite of Late Cretaceous age. The present geometry of the ore zones is tabular, with the thickest zones above depressions in the pluton-country rock contact. Analyses of high-grade ores from the mine define a 207 Pb/ 204 Pb- 235 U/ 204 Pb isochron indicating an age of mineralization of 51.0 + or - 0.5 m.y. This age coincides with a time of regional volcanic activity (Sanpoil Volcanics), shallow intrusive activity, erosion, and faulting. U-Th-Pb isotopic ages of zircons from the porphyritic quartz monzonite in the mine indicate an age of about 75 m.y., hence the present orebodies were formed about 24 m.y. after its intrusion. The 51-m.y. time of mineralization probably represents a period of mobilization and redeposition of uranium by supergene ground waters, perhaps aided by mild heating and ground preparation and preserved by a capping of newly accumulated, impermeable volcanic rocks. It seems most likely that the initial concentration of uranium occurred about 75 m.y. ago, probably from relatively mild hydrothermal fluids in the contact-metamorphic aureole of the U-rich porphyritic quartz monzonite.Pitchblende, coffinitc, pyrite, marcasite, and hisingerite are the most common minerals in the uranium-bearing veinlets, with minor sphalerite and chalcopyrite. Coffinitc with associated marcasite is paragenetically later than pitchblende, though textural and isotopic evidence suggests no large difference in the times of pitchblende and colfinite formation.The U-Pb isotope systematics of total ores and of pitchblende-coffinite and pyrite-marcasite separates show that whereas open system behavior for U and Pb is essentially negligible for large (200-500 g) ore samples, Pb migration has occurred on a scale of 1 to 10 mm (out of pitchblende and coffinite and into pyrite and marcasite). Also, long-term continuous leakage of radioactive daughters of 238 U (probably 222 Rn) has occurred on scales of from approximately 100 mu m approximately 10 cm. The isotopic composition of unsupported radiogenic Pb in pyrite-marcasite seems to depend on the mineralogical microenvironment of the grains, so that the radiogenic Pb in pyrite-marcasite intimately intermixed with pitchblende-coffinite tends to be deficient in 206 Pb, and the radiogenic Pb in pyrite-marcasite in gangue tends to have excess 206 Pb. These systematics probably reflect differences between the average distances of Pb and 222 Rn diffusion since the formation of the ores.

Washington

Age of uranium mineralization at the Jabiluka and Ranger deposits, Northern Territory, Australia: New U-Pb isotope evidence

The Ranger and Jabiluka uranium deposits are the largest in the Alligator Rivers uranium field, which contains at least 20 percent of the world's low-cost uranium reserves. Ore occurs in early Proterozoic metasediments, below an unconformity with sandstones of the 1.65-b.y.-old Kombolgie Formation. This study has used U-Pb isotope data from a large number of whole-rock drill core samples with a variety of mineral assemblages and textures. Ranger samples indicate a well-defined age of 1,737 + or - 20 m.y., consistent with earlier suggestions of the antiquity of this deposit. This age is distinctly pre-Kombolgie, so the Ranger deposit cannot have been formed by processes requiring its presence. The age is consistent, however, with mineralization related to heating associated with either the emplacement of early postmetamorphic granites, or possibly, with intrusion of the nearby Oenpelli Dolerite. In contrast, data for the least-altered Jabiluka ores yield a concordia intercept age of 1,437 + or - 40 m.y.--significantly younger than the Ranger age and also younger than the Kombolgie Formation. This age may correspond to a regional thermal event, as indicated both by mafic dikes of roughly this age and a zircon lower intercept age from a nearby granite-gneiss. Thus our data indicate that there must be at least three distinct periods of major U mineralization in the Alligator Rivers uranium field (including the previously determined approximately 900-m.y. age of the Nabarlek deposit), despite the fact that all of the deposits share strong similarities in their host rock, mineralogy, alteration, and geologic setting.Both Ranger and Jabiluka reflect a common, profound isotopic disturbance at about 400 to 600 m.y. This disturbance, which was especially pronounced at Jabiluka, may correspond to the development of basins and associated basalt flows to the west and southwest, as suggested by Crick et al. (1980).

Economic Geology

Geochemistry of vanadium in an epigenetic, sandstone-hosted vanadium-uranium deposit, Henry Basin, Utah

The epigenetic Tony M vanadium-uranium orebody in south-central Utah is hosted in fluvial sandstones of the Morrison Formation (Upper Jurassic). Although the deposit is mined for uranium, vanadium has a higher average abundance in the ore. Thus, the geochemistry of vanadium in the orebody was studied to characterize ore-forming processes within the inferred ground-water flow regime. Measurements of the relative amounts of V (super +3) and V (super +4) in ore minerals show that V (super +3) is more abundant. Thermodynamic calculations show that vanadium was more likely transported to the site of mineralization as V (super +4) . The ore formed as V (super +4) was reduced by hydrogen sulfide, followed by hydrolysis and precipitation of V (super +3) in oxide minerals (e.g., montroseitc or paramontroseite) or chlorite. Uranium was transported as uranyl ion (U (super +6) ), or some complex thereof, and reduced by hydrogen sulfide, forming coffinite. Detrital organic matter in the rocks served as the carbon source for sulfate-reducing bacteria. It was this bacteriogenic H 2 S that reduced the metals in the mineralization process.Possible sources for the V and U in this deposit have been identified previously. Vanadium most likely was derived from the dissolution of iron-titanium oxides, which liberated Fe as well as V. A zone of titanium-rich remnants is observed updip and up the hydrologic gradient from the deposit (M. Goldhaber and R. L. Reynolds, unpub. data). Uranium probably was derived from the overlying Brushy Basin Member of the Morrison Formation (Northrop, 1982). A preliminary age date for the deposit of 115 Ma (K. Ludwig, 1986, pers. commun.) indicates that the ore formed after deposition of the Brushy Basin Member.Previous studies have shown that the ore formed at the density-stratified interface between a basinal brine and dilute meteoric water. The mineralization processes described above occurred within the mixing zone between these two fluids. Stable isotope analyses of ore-stage dolomite show a progressively heavier carbon and oxygen isotope signature with increasing depth through an ore horizon, consistent with the two-solution interface model.

Economic Geology

Seasonal uranium distributions in the coastal waters off the Amazon and Mississippi Rivers

The chemical reactivity of uranium was investigated across estuarine gradients from two of the world’s largest river systems: the Amazon and Mississippi. Concentrations of dissolved (<0.45 μm) uranium (U) were measured in surface waters of the Amazon shelf during rising (March 1990), flood (June 1990) and low (November 1991) discharge regimes. The dissolved U content was also examined in surface waters collected across estuarine gradients of the Mississippi outflow region during April 1992, August 1993, and November (1993). All water samples were analyzed for U by isotope dilution inductively coupled plasma mass spectrometry (ICP-MS). In Amazon shelf surface waters uranium increased nonconservatively from about 0.01 μg I −1 at the river’s mouth to over 3 μg I −1 at the distal site, irrespective of river discharge stage. Observed large-scale U removal at salinities generally less than 15 implies a) that riverine dissolved U was extensively adsorbed by freshly-precipitated hydrous metal oxides (e.g., FeOOH, MnO 2 ) as a result of flocculation and aggregation, and b) that energetic resuspension and reworking of shelf sediments and fluid muds on the Amazon shelf released a chemically reactive particle/colloid to the water column which can further scavenge dissolved U across much of the estuarine gradient. In contrast, the estuarine chemistry of U is inconclusive within surface waters of the Mississippi shelf-break region. U behavior is most likely controlled less by traditional sorption and/or desorption reactions involving metal oxides or colloids than by the river’s variable discharge regime (e.g., water parcel residence time during estuarine mixing, nature of particulates, sediment storage and resuspension in, the confined lower river), and plume dispersal. Mixing of the thin freshwater lens into ambient seawater is largely defined by wind-driven rather than physical processes. As a consequence, in the Mississippi outflow region uranium predominantly displays conservative behavior; removal is evident only during anomalous river discharge regimes. ‘Products-approach’ mixing experiments conducted during the Flood of 1993 suggest the importance of small particles and/or colloids in defining a depleted U versus salinity distribution.

Louisiana