Nitrification processes in groundwaters evidenced by modification on the U contents and U-234/U-238 activity ratios

Groundwaters from the Botucatu-Piramboia aquifer system located at the Parana sedimentary basin in Brazil and sampled at Ribeirao Preto city, São Paulo State, were chemically and isotopically analysed, with the aim of evaluating how uranium isotopes U-234 and U-238 can be utilized to monitor the progress of nitrate, the main indicator of agrichemical pollution into an aquifer. Based on the isotope dilution analysis, the U-234/U-238 activity ratio and U content data in the groundwaters were utilized to deduce their proportions in a mixture, suggesting that the water not affected significantly by nitrification still dominates the exploitation system involving the studied wells.

A laboratory study of the transfer of U-234 and U-238 during water-rock interactions in the Carnmenellis granite (Cornwall, England) and implications for the interpretation of field data

Laboratory time-scale experiments were conducted on gravels from the Carnmenellis granite, Cornwall, England, with the purpose of evaluating the release of natural uranium isotopes to the water phase. The implications of these results for the production of enhanced U-234/U-238 activity ratios in Cornish groundwaters are discussed. It is suggested that the U-234/U-238 lab data can be used to interpret activity ratios from Cornwall, even when the observed inverse relationship between dissolved U and U-234/U-238 in leachates/etchates is taken into account. (C) 2001 Elsevier B.V. Ltd. All rights reserved.

Hydro(radio)chemical relationships in the giant Guarani aquifer, Brazil

This investigation was carried out within the Parana sedimentary basin and involved the sampling of 78 pumped tubular wells for evaluating the hydrochemistry and radioactivity due to the nuclides (238)U, (234)U, (222)Ra, (226)Ra, and (228)Ra in the Brazilian part of Guarani aquifer. Several significant correlations were found involving the geostatic pressure, for instance, specific flow rate, CO(3)(2-), SO(4)(2-) temperature, dissolved O(2), free CO(2), pH, redox potential Eh, conductivity, Na, HCO(3)-, CO(3)(2-) , SI(calcite), Cl(-), F(-), SO(4)(2-), and B. Carbonates precipitation was evidenced by inverse correlation between CO(3)(2-) and Ca, Mg, Sr, and Ba, whereas Na exhibited an opposite trend, dissolving rather than precipitating with increasing CO(3)(2-) concentration. An inverse correlation between 3 and K was found, possibly related to the increasing tendency of K to recombine with the thickness of the clayey layers. HCO(3)-played an important role on Na, Ca, Mg, and Sr dissolution. The dissolved U content and (234)U/(238)U activity ratio data were plotted on a two-dimensional diagram that was successfully utilized on identifying an unreported zone of U accumulation, though not necessarily of economic size and grade. The variability in chemical and radionuclides data indicated an important influence of the underlying Paleozoic sediments in the composition of waters from Guarani aquifer. The available data allowed estimate the groundwater residence time by two U-isotopes disequilibrium methods. Values of 45-61 ka were initially calculated, depending on the adopted porosity (15-20%), but a longer residence time (- 640 ka) was also estimated, which is more compatible with the hydraulic conductivity data in Guarani aquifer and groundwater flow velocity occurring at Milk River aquifer, Alberta, Canada. Such time range agrees with previously reported (14)C ages exceeding 30 ka BP at the more central parts of the Parana sedimentary basin. (c) 2005 Elsevier B.V. All rights reserved.

U-ages in soils and groundwater evidencing wet periods 400-600 kyr ago in southeast Brazil

U-238 and its radiogenic daughter U-234 have been utilized for dating soil formation and groundwater residence time during the last 1.5 million years, in this case based on the U-clissolution/precipitation occurring during modifications of the oxidation-reduction conditions. In this paper, we report a 400-600 kyr proxy of wet periods from sediments occurring in a soil profile developed over rocks outcropping at the Parana sedimentary basin in Brazil, and from groundwater exploited of Guarani aquifer at the same basin. The approaches indicated successful use of the U-modeled ages for suggesting wet periods exceeding the past 116-210 kyr from previous studies. (C) 2007 Elsevier Ltd. All rights reserved.

Health risk related to radon in a thermal spa utilizing waters from Guarani aquifer

This investigation was carried out within the Parana sedimentary basin, Brazil, involved the sampling of groundwater and air, and was realized with the purpose of evaluating the radioactivity, due to radon gas, in a thermal spa utilizing the waters from Guarani (Botucatu-Piramboia) aquifer. The results reported here provide additional information relative to that of previous studies focusing on the presence of radionuclides in the aquifer, which have mainly characterized those belonging to uranium and thorium series decay, such as the uranium isotopes (U-238 and U-234), radium isotopes (Ra-226 and Ra-228), radon daughters (Bi-214 and Pb-214) and radon (Rn-222) itself the results obtained were compared with the maximum permissible concentration limits in air and drinking water defined by international standards, such as the guidelines for drinking water quality established by the World Health Organization. The possible processes responsible for the presence of radon in the aquifer were also considered in order to evaluate the data obtained.

Determination of weathering rate of the Morro do Ferro Th-REEs deposit, Brazil using U-isotope method

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Geo(anthropo)genic factors affecting the radioactivity in groundwaters from Guarani aquifer, Brazil

This investigation was carried out within the Paraná sedimentary basin, involved the sampling of 77 pumped tubular wells, and was realized with the puipose of evaluating the radioactivity in the Brazilian part of Guarani (Botucatu-Pirambóia, Tacuarembó, Misiones) aquifer. The radioactivity due to nuclides belonging to uranium and thorium series decay was investigated in terms of the uranium isotopes 234U and 238U, radon (222Rn), and the radium isotopes 226Ra and 228Ra. The obtained results were compared with the maximum permissible concentration limits in drinking water defined by the Brazilian national standard, as well with the guidelines for drinking water quality established by the World Health Organization. The importance of water-rock/soil interactions was considered in order to explain most of the obtained data.

Avaliação do intemperismo químico e influências antropogênicas na bacia do Alto Sorocaba (SP)

Pós-graduação em Geologia Regional - IGCE

Estudo hidroquímico e dos isótopos de urânio nas águas subterrâneas em cidades do Estado do Amazonas (AM)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Selektiver Nachweis von Uran-236 mittels hochauflösender Resonanzionisations-Massenspektrometrie

Die vorliegende Dissertation beschreibt die Entwicklung, den Aufbau und die Erprobung eines neuartigen lasermassenspektrometrischen Nachweises des Ultraspurenisotops 236U. Das Nuklid 236U wird vorwiegend in Kernreaktoren durch Neutroneneinfang aus 235U gebildet und dient damit als Schlüsselisotop zur Unterscheidung anthropogenen Urans von natürlichem Uran-Vorkommen. Mit seinem Nachweis wird die Untersuchung der Migration von Kernbrennstoff in der Umwelt und die Beantwortung kritischer Fragen in der nuklearen Forensik ermöglicht. Im Rahmen dieser Arbeit wurde das Verfahren der hochauflösenden Resonanzionisations-Massenspektrometrie auf die Anforderungen des selektiven Nachweises von Uran-Isotopen angepasst. Wesentliche Schritte waren hierbei die Untersuchung einer effizienten Atomisation von Uran-Proben, die Identifikation atomarer und autoionisierender Zustände für eine resonante Anregungsleiter, die vollständige Spezifikation der Anregungsleiter für alle Uran-Isotope und schließlich die Umsetzung der Erkenntnisse in ein analytisches Messverfahren. Die optische Selektivität des Verfahrens konnte durch Dichtematrixrechnungen zu ca. 14 Größenordnungen abgeschätzt werden; die Nachweisgrenze des Verfahrens für das Isotopenverhältnis 236U / 238U ist dabei gegenwärtig durch Untergrund begrenzt und beträgt ca. 3 · 10−8. Mit diesen Spezifikationen konnte die Linearität und Präzision des Nachweisverfahrens über einen dynamischen Bereich von vier Größenordnungen nachgewiesen werden.

Diodenlaserbasierte Resonanzionisations-Massenspektrometrie zur Spektroskopie und Ultraspurenanalyse an Uranisotopen

In dieser Arbeit wird die Erweiterung und Optimierung eines Diodenlasersystems zur hochauflösenden Resonanzionisationsmassenspektrometrie beschrieben. Ein doppelinterferometrisches Frequenzkontrollsystem, welches Absolutstabilisierung auf ca. 1 MHz sowie sekundenschnelle Frequenzverstimmungen um mehrere GHz für bis zu drei Laser parallel ermöglicht, wurde optimiert. Dieses Lasersystem dient zwei wesentlichen Anwendungen. Ein Aspekt waren umfangreiche spektroskopische Untersuchungen an Uranisotopen mit dem Ziel der präzisen und eindeutigen Bestimmung von Energielagen, Gesamtdrehimpulsen, Hyperfeinkonstanten und Isotopieverschiebungen sowie die Entwicklung eines effizienten, mit kommerziellen Diodenlasern betreibbaren Anregungsschemas. Mit diesen Erkenntnissen wurde die Leistungsfähigkeit des Lasermassenspektrometers für die Ultraspurenanalyse des Isotops 236U, welches als Neutronendosimeter und Tracer für radioaktive anthropogene Kontaminationen in der Umwelt verwendet wird, optimiert und charakterisiert. Anhand von synthetischen Proben wurde eine Isotopenselektivität von 236U/238U=4,5(1,5)∙10-9 demonstriert.

Calcium concentrations and isotopic composition in carbonates and porefluids from ODP Hole 130-807A

The calcium isotopic compositions (d44Ca) of 30 high-purity nannofossil ooze and chalk and 7 pore fluid samples from ODP Site 807A (Ontong Java Plateau) are used in conjunction with numerical models to determine the equilibrium calcium isotope fractionation factor (a_s-f) between calcite and dissolved Ca2+ and the rates of post-depositional recrystallization in deep sea carbonate ooze. The value of a_s-f at equilibrium in the marine sedimentary section is 1.0000+/-0.0001, which is significantly different from the value (0.9987+/-0.0002) found in laboratory experiments of calcite precipitation and in the formation of biogenic calcite in the surface ocean. We hypothesize that this fractionation factor is relevant to calcite precipitation in any system at equilibrium and that this equilibrium fractionation factor has implications for the mechanisms responsible for Ca isotope fractionation during calcite precipitation. We describe a steady state model that offers a unified framework for explaining Ca isotope fractionation across the observed precipitation rate range of ~14 orders of magnitude. The model attributes Ca isotope fractionation to the relative balance between the attachment and detachment fluxes at the calcite crystal surface. This model represents our hypothesis for the mechanism responsible for isotope fractionation during calcite precipitation. The Ca isotope data provide evidence that the bulk rate of calcite recrystallization in freshly-deposited carbonate ooze is 30-40%/Myr, and decreases with age to about 2%/Myr in 2-3 million year old sediment. The recrystallization rates determined from Ca isotopes for Pleistocene sediments are higher than those previously inferred from pore fluid Sr concentration and are consistent with rates derived for Late Pleistocene siliciclastic sediments using uranium isotopes. Combining our results for the equilibrium fractionation factor and recrystallization rates, we evaluate the effect of diagenesis on the Ca isotopic composition of marine carbonates at Site 807A. Since calcite precipitation rates in the sedimentary column are many orders of magnitude slower than laboratory experiments and the pore fluids are only slightly oversaturated with respect to calcite, the isotopic composition of diagenetic calcite is likely to reflect equilibrium precipitation. Accordingly, diagenesis produces a maximum shift in d44Ca of +0.15? for Site 807A sediments but will have a larger impact where sedimentation rates are low, seawater circulates through the sediment pile, or there are prolonged depositional hiatuses.

Geochemistry on manganese deposit from the Median Valley of the Mid-Atlantic Ridge

A manganese oxide crust from an extensive deposit in the median valley of the Mid-Atlantic Ridge was found to be unusually high in manganese (up to 39.4% Mn), low in Fe (as low as 0.01% Fe), low in trace metals and deficient in Th230 and Pa231 with respect to the parent uranium isotopes in the sample. The accumulation rate is 100 mm to 200 mm/10 million year, or 2 orders of magnitude faster than the typical rate for deep-sea ferromanganese deposits. The rapid growth rate and unusual chemistry are consistent with a hydrothermal origin or with a diagenetic origin by manganese remobilized from reduced sediments. Because of the association with an active ridge, geophysical evidence indicative of hydrothermal activity, and a scarcity of sediment in the sampling area, we suggest that a submarine hot spring has created the deposit.