The main aim of this work was to investigate the extent of uranium and radium -fixation and mobilization at the interface of mining influenced surface water and sub-hydric soils, sediment and plant detritus. A freshwater ecosystem (stream channels in an alder swamp forest – Alno-Lemnetum with low residence time shallow ponds) developed directly below a mining site (Neuensalz) and influenced by uranium containing water served as investigation site for the identification of possible fixation and mobilization mechanisms. In addition, investigations were carried out on sediments in a water reservoir downstream of the examined abandoned mining site. It could be shown, that radium concentrations of the examined surface water (2001 – 2004) are only slightly higher compared to the range of geogenic levels for German surface waters, and that its activity concentrations decreased along the investigated flow path. In contrast, uranium concentrations are well above geogenic levels and the concentration level stays high along the whole water pathway through the study area. The U-238:Ra-226 ratio of the examined surface water from the spring to a pond outflow significantly increased. The uranium chain activity concentrations in the sediments determined in this study partly exceeded considerably the regional geogenic level. For the sediment water the 238U: 226Ra ratio in the first part of the flow path is significantly shifted in favor of radium while in the second part the ratio is shifted in favor of uranium. There were indications that the dissolved uranium is transported in the form of soluble carbonate complexes. Radium however is rather fixed under dominantly oxidizing conditions along the mainly turbulent mixed shallow water pathway. The fixation of uranium and radium in the upper section of the pathway (direct below the spring) was found to be inorganically, whereas in the second part organic bonds are more indicated. The influence of allochthonous organic carbon as main metabolic energy source for low order lotic ecosystems on the fixation of uranium was investigated by analyzing, the effects of leaves (coarse particulate organic matter: CPOM) and their degradation products (mainly fine particulate organic matter: FPOM and biofilms etc.). It was found that the highly mobile fraction of uranium in the water pathway, preferably present under the given conditions in the form different uranyl-carbonato-complexes, is efficiently fixed on fresh organic plant material (plant litter, leaves) in the first steps of organic matter decomposition within a few days. But it also can be immobilized relatively stable. It was also found that CPOM is a temporary sink for uranium, which may be sedimented depending on the turbulence flow and discharge. This may contribute to the directional removal of uranium from the water into the sediment. Finally this work analyzed the conditions in the pelagic and benthic zone of the Neuensalz pre dam of the Pöhl reservoir, which is located downstream of the mining site. It presents a periodically stagnant water body with seasonally continuous sedimentation, a possible stable sink of uranium and products of radioactive decay in early diagenesis. Water samples of the pelagic zone and undisturbed sediment cores were taken and analyzed during winter stagnation. The results are discussed in front of seasonal changes in water chemistry and load data. U-238 and Ra-226 showed a culmination of activity concentrations in the sediment horizons from 25 to 35 cm depth, in particular at a centrally located sampling point (K3). At this point highest activity concentrations of 238U were found with a median value of 770 Bq*kg-1 at a depth of 30 cm. At the same location 226Ra shows activity concentrations of 250 Bq*kg-1(median). Based on the Cs-137 dating method a sedimentation rate of 1.5 cm*yr-1 was calculated for the pre-dam Neuensalz sediment. On average sedimentation rates for 238U of 3,7 ± 1,1 kBq*m-2*yr-1 and for 226Ra of 3,5 ± 0,5 kBq*m-2*yr-1 were calculated. Furthermore, a total uranium stock of 68 ± 6 kg per hectare in the sediment was estimated. In connection with a sedimentation period of 23 years, the uranium inventory in the sediments would correspond to a portion of approx. 18 % of the uranium feed by the water influx estimated for the same period. This estimation did not take into account a geogenic portion and other sources like fertilizer. For radium, the situation is reversed. An extrapolation of the cumulative load for the same period results in a lower value by almost a factor of 100 compared to uranium. This compares with a radium inventory in the sediment, which is about 15 times higher than the projected load. This leads to the conclusion that in addition to the supply from the mining legacy also the geogenic background and/or discontinuous particulate import (via storm water stream runoff etc.) has to be considered. The analysis of the bonding stability and related potential mobilization of the sedimentary uranium using sequential chemical extraction shows that most of the uranium is found in the organic fraction over the entire sediment layer, which may be identified as organically bound or as uraninite. In conclusion not only radium is immobilized near to the source but also a relevant share of uranium is permanently fixed even in/on durably deposited organic matter despite eu-trophic conditions with high nitrate load, traceable in deeper sediment layers due to e.g intensive land use.:Inhaltsverzeichnis 1 Einleitung und Zielstellung............................................................1 2 Stand des Wissens.......................................................................7 2.1 Natürliche Radionuklide in der Umwelt............................................7 2.1.1 Uran Vorkommen und Verhalten in der Umwelt..............................9 2.1.2 Radium Vorkommen und Verhalten in der Umwelt........................19 3 Material und Methoden...............................................................22 3.1 Untersuchungsgebiet..................................................................22 3.2 Probenahme und Probenvorbereitung...........................................25 3.2.1 Untersuchungen zur Radionuklidverteilung im Abstrom des ehemaligen Uranbergbaugebiets Neuensalz............................................................25 3.2.2 Untersuchungen zur Uranfixierung an abgebautem organischen Substrat...........................................................................................26 3.2.3 Sedimentbeprobung in der Vorsperre Neuensalz............................29 3.3 Analytische Verfahren.................................................................35 3.3.1 Physikalisch-chemische Charakterisierung der Blattproben..............35 3.3.2 Physikalisch-chemische Charakterisierung der Sedimente................38 3.3.3 Mikrowellenaufschluss ................................................................44 3.3.4 Instrumentalanalytische Verfahren...............................................44 3.4 Mathematische Verfahren...........................................................47 3.4.1 Berechnung der Sedimentationsrate.............................................47 3.4.2 Grafische Darstellung der Daten..................................................47 3.4.3 Statistische Berechnungen..........................................................48 4 Ergebnisse und Diskussion..........................................................49 4.1 Auswirkung zunehmender Einträge von Bestandesabfall auf die Festlegung von Radionukliden.............................................................49 4.1.1 Quellen- und Oberflächenwasser..................................................49 4.1.2 Radioaktivitätskonzentration (238U, 226Ra, 210Pb) im Oberflächenwasser entlang der Fließstrecke..........................................54 4.1.3 Urantransportverhalten im Oberflächenwasser entlang der Fließstrecke......................................................................................56 4.1.4 Räumliche Verteilung von Radionukliden (238U, 226Ra und 210Pb) im Gewässersediment entlang der Fließstrecke..........................................60 4.1.5 Maßgebliche Einflussfaktoren für die Fixierung von Radium im Gewässersediment entlang der Fließstrecke..........................................64 4.1.6 Maßgebliche Einflussfaktoren für die Fixierung von Uran im Gewässersediment entlang der Fließstrecke..........................................65 4.2 Einfluss von allochthonem organischen Kohlenstoff und seinen Abbauprodukten auf die Festlegung von Radionukliden...........................69 4.2.1 Anreicherung der Radionuklide 238U, 226Ra, 210Pb sowie 137Cs an der organischen Substanz (CPOM) während des Abbauprozesses.............69 4.2.2 Organisches Material als Senke für Uran während des Abbauprozesses................................................................................71 4.2.3 Spezifischer Einfluss von partikulärem Material und polymeren Kohlenstoffverbindungen im Verlaufe des Laubabbaus auf die Uranfixierung....................................................................................73 4.2.4 Bedeutung des abiotischen Einflusses auf die Uranfestlegung während des Abbauversuches von Laub im Fließgewässer....................................80 4.2.5 Transportverhalten von Uran während des Abbauversuches im Fließgewässer...................................................................................82 4.3 Sediment der Standgewässer als Senke von Uran und seinen Tochternukliden................................................................................87 4.3.1 Radionuklidkonzentration in rezenten Sedimenten der Vorsperre Neuensalz.........................................................................................87 4.3.2 Einflussfaktoren auf die Verteilung von Uran zwischen dem Porenwasser und der Festphase der Sedimente.....................................98 4.3.3 Bindungsformen von Uran und begleitenden Elementen im Sediment........................................................................................117 5 Zusammenfassende Diskussion, Schlussfolgerungen und Ausblick..124 6 Zusammenfassung...................................................................131 7 Literaturverzeichnis..................................................................137 8 Anhang...................................................................................175 / Hauptziel der vorliegenden Arbeit war die Untersuchung des Umfangs der Festlegung bzw. Mobilisierung von Uran und Radium an der Grenzfläche von Bergbau beeinflußtem Oberflächenwasser und subhydrischen Böden, Sedimenten sowie Bestandsabfall (Detritus). Als Untersuchungsgebiet zur Identifizierung entsprechender Fixierungs- und Mobilisierungsmechanismen diente ein Süßwasser - Ökosystem (Bach in einem Erlenbruchwald – Alno-Lemnetum – und integrierte flache Teiche mit geringer Verweilzeit) unterhalb eines ehemaligen Uranerzbergbau-Gebietes (Neuensalz), das von uranhaltigem Wasser durchströmt ist. Darüber hinaus Sedimentanalysen eines periodisch stagnierenden Wasserkörpers (Vorsperre der Talsperre Pöhl) im Abstrombereich der untersuchten Bergbaualtlast vorgenommen. Es konnte gezeigt werden, dass die Radiumkonzentration des Oberflächenwassers (2001-2004) geringfügig über der des geogenen Niveaus für deutsche Oberflächenwässer liegt und dass die entsprechende Aktivitätskonzentration von Radium entlang der untersuchten Fließstrecke beginnend mit einer Quelle an einem Tailingdamm deutlich abnimmt. Dagegen liegen die Urankonzentrationen des Oberflächenwassers deutlich über dem geogenen Hintergrund. Seine Aktivitätskonzentrationen bleiben entlang der Fließstrecke weitgehend stabil. Das 238U:226Ra-Verhältnis des Oberflächenwassers wird sich entlang der Fließstrecke von der Quelle unterhalb des Tailingdammes bis zum Abfluss aus der ersten, schwächer durchflossenen kleinen Senke (Forellenteich) erhöht. Die in dieser Arbeit ermittelten Aktivitätskonzentrationen der untersuchten Nuklide der Sedimente lagen zum Teil erheblich über dem geogenen Niveau der Region. Das 238U:226Ra-Verhältnis des Bachsediments ist im ersten Teil der Fließstrecke deutlich zugunsten des Radiums verschoben, während es im zweiten Teil zugunsten von Uran verschoben ist. Dies weist darauf hin, dass das gelöste Uran in Form carbonatischer Komplexe transportiert wird. Radium wird dagegen unter den vorherrschenden oxidierenden Bedingungen entlangder Fließstrecke eher fixiert. Für die Festlegung von Uran und Radium wurde im oberen Teil der Fließstrecke (direkt unterhalb der Quelle) eher auf anorganische Bindungen geschlossen, während die Fixierung im zweiten Teil der Fließstrecke eher organischer Natur ist. Da im Oberlauf von Fließgewässern allochthoner organischer Kohlenstoff die wesentliche die Energiequelle für alle Ökosystemfunktionen bildet und eine besondere Funktion mit Blick auf Untersuchungsziel vermutet werden kann, wurde die Wirkung von Laub (grob- organisches Material: CPOM) und seinen Abbauprodukten (fein-partikuläres organisches Material: FPOM, Biofilm usw.) auf die Fixierung von Uran analysiert. Es wurde festgestellt, dass das im Wasserpfad sehr mobile Uran, welches unter den gegebenen Bedingungen vorzugsweise in verschiedenen Uranyl-Carbonato-Komplexen vorliegt, nicht nur an frischer organischer Substanz pflanzlichen Ursprungs (Bestandesabfall, Laub) im Verlauf biologischen Abbaus effizient gebunden und festgelegt wird, sondern auch sehr stabil immobilisiert werden kann. Es wurde auch ermittelt, dass CPOM ein temporärer Speicher für Uran ist, welcher je nach Fließgeschwindigkeit sedimentieren und damit zum gerichteten Transfer von Uran aus dem Wasser in das Sediment beitragen kann. Der anteilige Austrag über das verstärkt gebildete DOC über den Laubeintrag ist relativ gering. Schließlich wurden die Verhältnisse mit Bezug zur Fragestellung in der pelagischen und benthischen Zone der Vorsperre Neuensalz der Talsperre Pöhl analysiert, die stromabwärts des Bergbaugebietes anschießt. Die Vorsperre stellt einen periodisch stagnierenden Wasserkörper mit saisonaler kontinuierlicher Sedimentation dar und damit eine mögliche stabile Senke für Uran und seine radioaktiven Zerfallsprodukte in der Frühdiagenese. Wasserproben der pelagischen Zone und ungestörte Sedimentkerne wurden in der Phase der Winterstagnation entnommen, analysiert und unter Berücksichtigung saisonaler Unterschiede bezüglich Wasserchemie und Frachtdaten disskutiert. Für U-238 und Ra-226 zeigt sich eine Kulmination der Aktivitätskonzentration in den mittleren Sediment- Horizonten von 25-35 cm Tiefe, insbesondere an der Probenahmestelle K3. Dort fanden sich auch die höchsten Aktivitätskonzentrationen der Vorsperre für 238U mit einem Medianwert von 770 Bq*kg-1 in einer Tiefe von 30 cm. Für Ra-226 fand sich am selben Ort eine Aktivität von 250 Bq*kg-1 (Median). Anhand der Datierung mithilfe der Cs-137 Methode wurde für das Sediment der Vorsperre Neuensalz eine Sedimentationsrate von 1,5 cm*a-1 errechnet. Für Uran ergab sich eine Sedimentationsrate von 3,7 ± 1,1 kBq*m-2*a-1 und für Ra-226 eine solche von 3,50 ± 0,5 kBq*m-2*a-1. Darüber hinaus wurde die im Schnitt ca. 40 cm mächtigen Sedimente ein Uranvorrat von 68 ± 6 kg pro Hektar bilanziert. In Verbindung mit der Dauer des Bilanzzeitraumes der Sedimentation (23 Jahre) entspräche das in der Vorsperre vorgefundene Uraninventar einem Anteil von ca. 18 % der für diesen Zeitraum abgeschätzten Uranfracht im Wasserzufluss, wobei der geogene Anteil des Urans und die Ausbringung von Phosphatdüngemitteln in den Sedimenten noch nicht berücksichtigt ist. Für Radium sind die Verhältnisse umgekehrt. Wenn aus den gegenwärtigen Aktivitätskonzentrationen im Zufluss auf eine kumulative Fracht für den 23-jährigen Bilanzierungs- bzw. Betrachtungszeitraum hochgerechnet wird, ergibt sich ein fast um den Faktor 100 geringerer Wert, verglichen mit Uran. Dem steht ein Radiuminventar im Sediment gegenüber, welches etwa 15-mal größer als diese hochgerechnete Fracht ist. Daraus ist abzuleiten, dass neben der relativ geringen wassergelösten Zufuhr aus der Bergbaualtlast dem gegogenen Hintergrund im sedimentierenden Substrat sowie diskontinuierlich Partikel (über Regenwasserabfluss) Bedeutung beizumessen ist. Bei der Analyse der Bindungsverhältnisse des sedimentären Urans (sequentielle Extraktion) wurde der größte Anteil des Urans im Sediment als Uraninit bzw. als organisch gebunden identifiziert. Insgesamt ist zu schließen, dass nicht nur Radium in der Nähe von Quellen immobilisiert wird, sondern auch Uran eine dauerhafte Fixierung in ständig abgelagertem organischem Material erfährt. Diese Fixierung ist trotz eutropher Bedingungen mit hoher Niratbelastung stabil und in tieferen Sedimentschichten nachweisbar.:Inhaltsverzeichnis 1 Einleitung und Zielstellung............................................................1 2 Stand des Wissens.......................................................................7 2.1 Natürliche Radionuklide in der Umwelt............................................7 2.1.1 Uran Vorkommen und Verhalten in der Umwelt..............................9 2.1.2 Radium Vorkommen und Verhalten in der Umwelt........................19 3 Material und Methoden...............................................................22 3.1 Untersuchungsgebiet..................................................................22 3.2 Probenahme und Probenvorbereitung...........................................25 3.2.1 Untersuchungen zur Radionuklidverteilung im Abstrom des ehemaligen Uranbergbaugebiets Neuensalz............................................................25 3.2.2 Untersuchungen zur Uranfixierung an abgebautem organischen Substrat...........................................................................................26 3.2.3 Sedimentbeprobung in der Vorsperre Neuensalz............................29 3.3 Analytische Verfahren.................................................................35 3.3.1 Physikalisch-chemische Charakterisierung der Blattproben..............35 3.3.2 Physikalisch-chemische Charakterisierung der Sedimente................38 3.3.3 Mikrowellenaufschluss ................................................................44 3.3.4 Instrumentalanalytische Verfahren...............................................44 3.4 Mathematische Verfahren...........................................................47 3.4.1 Berechnung der Sedimentationsrate.............................................47 3.4.2 Grafische Darstellung der Daten..................................................47 3.4.3 Statistische Berechnungen..........................................................48 4 Ergebnisse und Diskussion..........................................................49 4.1 Auswirkung zunehmender Einträge von Bestandesabfall auf die Festlegung von Radionukliden.............................................................49 4.1.1 Quellen- und Oberflächenwasser..................................................49 4.1.2 Radioaktivitätskonzentration (238U, 226Ra, 210Pb) im Oberflächenwasser entlang der Fließstrecke..........................................54 4.1.3 Urantransportverhalten im Oberflächenwasser entlang der Fließstrecke......................................................................................56 4.1.4 Räumliche Verteilung von Radionukliden (238U, 226Ra und 210Pb) im Gewässersediment entlang der Fließstrecke..........................................60 4.1.5 Maßgebliche Einflussfaktoren für die Fixierung von Radium im Gewässersediment entlang der Fließstrecke..........................................64 4.1.6 Maßgebliche Einflussfaktoren für die Fixierung von Uran im Gewässersediment entlang der Fließstrecke..........................................65 4.2 Einfluss von allochthonem organischen Kohlenstoff und seinen Abbauprodukten auf die Festlegung von Radionukliden...........................69 4.2.1 Anreicherung der Radionuklide 238U, 226Ra, 210Pb sowie 137Cs an der organischen Substanz (CPOM) während des Abbauprozesses.............69 4.2.2 Organisches Material als Senke für Uran während des Abbauprozesses................................................................................71 4.2.3 Spezifischer Einfluss von partikulärem Material und polymeren Kohlenstoffverbindungen im Verlaufe des Laubabbaus auf die Uranfixierung....................................................................................73 4.2.4 Bedeutung des abiotischen Einflusses auf die Uranfestlegung während des Abbauversuches von Laub im Fließgewässer....................................80 4.2.5 Transportverhalten von Uran während des Abbauversuches im Fließgewässer...................................................................................82 4.3 Sediment der Standgewässer als Senke von Uran und seinen Tochternukliden................................................................................87 4.3.1 Radionuklidkonzentration in rezenten Sedimenten der Vorsperre Neuensalz.........................................................................................87 4.3.2 Einflussfaktoren auf die Verteilung von Uran zwischen dem Porenwasser und der Festphase der Sedimente.....................................98 4.3.3 Bindungsformen von Uran und begleitenden Elementen im Sediment........................................................................................117 5 Zusammenfassende Diskussion, Schlussfolgerungen und Ausblick..124 6 Zusammenfassung...................................................................131 7 Literaturverzeichnis..................................................................137 8 Anhang...................................................................................175

No description available.

In this thesis, the response of uranium minerals and poorly crystalline phases to changes in geochemical conditions through geological time has been assessed in order to understand the mobility of natural uranium in the fracture network of a proposed site for a spent nuclear fuel repository in Forsmark, Sweden. Identification and characterization of solid phase uranium have been performed through electron microprobe analysis and optical petrography (Article I). The identified uraninite, haiweeite, and uranophane crystals have been dated using U-Pb and Pb-Pb isotope ratios obtained from secondary ion mass spectrometry and laser ablation-inductively coupled plasma-mass spectrometry (Article II). The mobility of uranium in current Forsmark groundwaters and fracture system has been modelled using the PHREEQC geochemical program and Ra and Rn isotope systematics (Article IV). The rate of submarine groundwater discharge (SGD) from the Forsmark coast to Öregrundsgrepen has also been modelled using Ra isotopes (Article V). Results from these studies support a geologically early (~1200 Ma) oxidation of U(IV) to U(VI). It is further suggested that the old U(VI) minerals present in the bedrock are soluble at the pe values and alkalinities observed in the Forsmark groundwaters. At pe &lt; −4.6 and alkalinity &lt; 60 mg/L, U(VI) can be reduced to U(IV) and deposited in the fracture network. Although a non-negligible rate of SGD has been observed, this cannot be attributed to the discharge of deep (&gt;200 m.b.s.l.) Forsmark groundwaters on the basis of current data. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 2: Manuscript. Paper 3: In press. Paper 4: Manuscript. Paper 5: Manuscript.</p>

Trusted Computing capability has become ubiquitous these days, and it is being widely deployed into consumer devices as well as enterprise platforms. As the number of threats is increasing at an exponential rate, it is becoming a daunting task to secure the systems against them. In this context, the software integrity measurement at runtime with the support of trusted platforms can be a better security strategy. Trusted Computing devices like TPM secure the evidence of a breach or an attack. These devices remain tamper proof if the hardware platform is physically secured. This type of trusted security is crucial for forensic analysis in the aftermath of a breach. The advantages of trusted platforms can be further leveraged if they can be used wisely. RADIUM (Race-free on-demand Integrity Measurement Architecture) is one such architecture, which is built on the strength of TPM. RADIUM provides an asynchronous root of trust to overcome the TOC condition of DRTM. Even though the underlying architecture is trusted, attacks can still compromise applications during runtime by exploiting their vulnerabilities. I propose an application-level integrity measurement solution that fits into RADIUM, to expand the trusted computing capability to the application layer. This is based on the concept of program invariants that can be used to learn the correct behavior of an application. I used Daikon, a tool to obtain dynamic likely invariants, and developed a method of observing these properties at runtime to verify the integrity. The integrity measurement component was implemented as a Python module on top of Volatility, a virtual machine introspection tool. My approach is a first step towards integrity attestation, using hypervisor-based introspection on RADIUM and a proof of concept of application-level measurement capability.

[pt] Quatro isótopos de rádio com diferentes tempos de meia-vida existem na natureza. Em água doce, o rádio aparece adsorvido ao material particulado enquanto que na água do mar o rádio apresenta um comportamento conservativo, sendo a concentração dos diferentes isótopos de rádio governada pelos processos de diluição, advecção e difusão, bem como pelo decaimento radioativo. Os quatro isótopos naturais de rádio são traçadores extensamente utilizados para determinar taxas de mistura de águas. No presente trabalho, desenvolvido no estuário do Rio Paraíba do Sul, os isótopos de rádio de meiavida curta (224Ra e 223Ra) foram determinados usando o sistema de contagem de coincidência com tempo de retardo (RaDeCCTM). Os isótopos de meia-vida longa (226Ra e 228Ra) foram determinados pela técnica de contagem alfa e beta totais, após a dissolução da fibra de MnO2 usada para a pré-concentração do rádio. Os resultados obtidos dos isótopos de meia-vida longa (226Ra e 228Ra) indicaram que a difusão é o processo dominante de suas distribuições até a distância de 32 km em relação à costa. A distribuição dos isótopos de meia- vida curta (223Ra e 224Ra) nesta região apresentaram um coeficiente de difusão de 13,9 km2d-1 e 15,1 km(2)d(-1) para a 1ª amostragem, realizada na estação seca, e de 59,1 km(2)d(-1) e 59,5 km(2)d(-1) para a 2ª amostragem, realizada na estação chuvosa. / [en] Four radium isotopes with different half life exist in the nature. In fresh waters, the radium appears adsorbed to the particulate material while in the sea water radium presents a conservative behavior, being the concentration of different isotopes of radium governed by the processes of dilution, advection and diffusion, as well as the radioactive decay. The four natural radium isotopes are tracers extensively used to determine taxes of water mixing. In the present work, developed in the Paraíba do Sul River Estuary, the short half life radium isotopes (224Ra and 223Ra) were determined using a delayed coincidence counting system (RaDeCCTM). The isotopes of long half life (226Ra and 228Ra) were determined by the technique of total alpha counting and beta, after the dissolution of the MnO2 fiber used to pre-concentrate radium. The results obtained of isotopes of long half life (226Ra and 228Ra) had indicated that the diffusion is the dominant process of its distributions until in the distance of 32 km in relation to the coast. The distribution of isotopes of short half life (224Ra and 223Ra) in this region had presented a diffusion coefficient of 13.9 km2d-1 and 15.1 km(2)d(-1) for 1ª sampling, was made in the dry season, and of 59.1 km(2)d(-1) and 59.5 km(2)d(-1) for second sampling, was made in the rainy season.

Este trabalho teve por objetivos estudar a distribuição das concentrações de atividade dos isótopos de rádio de meias-vidas longas, 226Ra e 228Ra, em amostras de águas minerais coletadas no Balneário de Caxambu (MG) e no Balneário de Águas de Lindóia (SP). Foram observadas concentrações de atividade de 228Ra relativamente aumentadas em relação às de 226Ra nas águas minerais estudadas no Balneário de Caxambu. As concentrações elevadas de carbonatos e bicarbonatos destas águas podem resultar em um conseqüente aumento da solubilidade dos isótopos de Ra e pode ter um papel importante para a distribuição do 228Ra e para as reações de equilíbrio entre as fases sólida e líquida das soluções. No Balneário de Caxambu, as concentrações de atividade médias aritméticas variaram de 83 mBq L-1 a 3599 mBq L-1 e de 60 mBq L-1 a 4481 mBq L-1 para 226Ra e 228Ra, respectivamente. O maior valor de atividade de 226Ra foi observado nas águas da Fonte Venâncio, enquanto que a concentração máxima de 228Ra foi determinada na Fonte Ernestina Guedes. As razões de atividade 228Ra/ 226Ra variaram de 0,079 (Fonte Conde DEau e Princesa Isabel) a 4,2 (Fonte Mairink II). Em Águas de Lindóia as concentrações de atividade médias aritméticas variaram de 4,6 mBq L-1 a 41 mBq L-1 e de 30 mBq L-1 a 54 mBq L-1 para 226Ra e 228Ra, respectivamente. O maior valor de atividade de 226Ra foi observado nas águas da Fonte Engarrafada São Jorge, enquanto que a concentração máxima de 228Ra foi determinada na Fonte Santa Filomena (torneira pública 2). As razões de atividade 228Ra/ 226Ra variaram de 1,2 (Fonte Engarrafada São Jorge) a 9,1 (Fonte Engarrafada Jatobá 1). A exposição de indivíduos do público à radiação natural em virtude do consumo das águas minerais também foi avaliada neste trabalho. As doses efetivas foram estimadas utilizando-se um modelo dosimétrico conservativo, e integrando-se os resultados ao longo de 70 anos de vida de um indivíduo adulto, após a incorporação de 226Ra e 228Ra. Os resultados desta avaliação radiossanitária demonstraram que o nível de referência de dose efetiva comprometida recomendado pela Organização Mundial de Saúde de 0,1 mSv a-1 foi ultrapassado em quase todas as fontes de Caxambu, exceto para a Fonte Viotti, Fonte Dom Pedro e Fonte Dona Leopoldina. Em Águas de Lindóia e Lindóia as maiores doses efetivas comprometidas obtidas foram 8,4 10-3 mSv a-1 para o 226Ra (Fonte engarrafada São Jorge) e 2,6 10-2 mSv a-1 para o 228Ra (Fonte Santa Filomena torneira pública 2). Estes valores são menores que o limite recomendado pela Organização Mundial de Saúde. Doses efetivas comprometidas de até 7,4 x 10-1 mSv a-1 para o 226Ra (Fonte Venâncio, Caxambu) e 2,2 mSv a-1 para o 228Ra (Fonte Ernestina Guedes, Caxambu) foram estimadas no presente trabalho. No caso do 226Ra, este valor representa menos que 31% da dose efetiva média anual atribuída a radioatividade natural. Contudo, no caso do 228Ra, o limite anual de dose efetiva comprometida recomendado pela ICRP (considerando-se todas as fontes de exposição da população mundial à radiação) foi excedido não só na Fonte Ernestina Guedes, mas também na Fonte Beleza. / The aim of this work was to study the long-lived Ra isotopes, 226Ra and 228Ra, natural distribution in mineral and spring waters from Caxambu (MG) and Águas de Lindóia (SP) waterparks. In Caxambu mineral waters it was observed 228Ra acitivity concentrations slightly higher than those of 226Ra. The elevated content of carbonates and bicarbonates of these waters can result in an increased solubility of the both Ra isotopes and may play an important role for the fate of 228Ra and its equilibrium distribution between solid and liquid phases. In Caxambu Thermal Spa, arithmetic mean activities ranged from 83 mBq L-1 to 3599 mBq L-1 and from 60 mBq L-1 to 4481 mBq L-1 for 226Ra and 228Ra, respectively. The highest 226Ra activity was found in Venancio Spring, while the maximum 228Ra activity value was determined in Ernestina Guedes. 228Ra/ 226Ra activity ratios varied from 0.079 (Conde DEau and Princesa Isabel Spring) to 4.2 (Mairink II Spring). In Águas de Lindóia, arithmetic mean activities ranged from 4.6 mBq L-1 to 41 mBq L-1 and from 30 mBq L-1 to 54 mBq L-1 for 226Ra and 228Ra, respectively. The maximum 226Ra activity concentration was found in the bottled mineral water São Jorge, while the higher 228Ra activity concentration was determined in Santa Filomena Spring (public station 2). 228Ra/ 226Ra activity ratios varied from 1.2 (bottled mineral water São Jorge) to 9.1 (bottled mineral water Jatobá 1). This work also performed the dose assessment due to the ingestion of 226Ra and 228Ra in Caxambu and Águas de Lindóia mineral and spring waters. The committed effective doses were estimated by using a conservative dosimetric model and taking into account the results over a lifetime (70 years) following intake of both long-lived Ra isotopes. The results from this radiological evaluation showed that the guindance committed effective dose level of 0.1 mSv y-1 recommended by World Health Organization was exceeded in almost all samples studied in Caxambu, except for Viotti Spring, Dom Pedro Spring and Dona Leopoldina Spring. In Águas de Lindóia and Lindóia, the highest committed effective doses estimated were 8.4 10-3 mSv y-1 for the intake of 226Ra (bottled mineral water São Jorge) and 2.6 10-2 mSv y-1 for 226Ra (Santa Filomena spring station 2). Both values are below the limit recommended by World Health Organization. The maximum commited effective doses per year obtained in this work were 7.4 10-1 mSv y-1 for 226Ra (Venancio Spring) and 2.2 mSv y-1 for 228Ra (Ernestina Guedes Spring). Considering the case of 226Ra intake via mineral water, the dose obtained represents less than 31 % of the average effective dose attributable annually from natural background radiation. However, in the case of 228Ra the annual committed effective dose limit recommended by ICRP (considering all sources of radiation exposure for the world population) was exceeded not only in Ernestina Guedes Spring, but also in Beleza Spring.

Este trabalho teve por objetivos estudar a distribuição das concentrações de atividade dos isótopos de rádio de meias-vidas longas, 226Ra e 228Ra, em amostras de águas minerais coletadas no Balneário de Caxambu (MG) e no Balneário de Águas de Lindóia (SP). Foram observadas concentrações de atividade de 228Ra relativamente aumentadas em relação às de 226Ra nas águas minerais estudadas no Balneário de Caxambu. As concentrações elevadas de carbonatos e bicarbonatos destas águas podem resultar em um conseqüente aumento da solubilidade dos isótopos de Ra e pode ter um papel importante para a distribuição do 228Ra e para as reações de equilíbrio entre as fases sólida e líquida das soluções. No Balneário de Caxambu, as concentrações de atividade médias aritméticas variaram de 83 mBq L-1 a 3599 mBq L-1 e de 60 mBq L-1 a 4481 mBq L-1 para 226Ra e 228Ra, respectivamente. O maior valor de atividade de 226Ra foi observado nas águas da Fonte Venâncio, enquanto que a concentração máxima de 228Ra foi determinada na Fonte Ernestina Guedes. As razões de atividade 228Ra/ 226Ra variaram de 0,079 (Fonte Conde DEau e Princesa Isabel) a 4,2 (Fonte Mairink II). Em Águas de Lindóia as concentrações de atividade médias aritméticas variaram de 4,6 mBq L-1 a 41 mBq L-1 e de 30 mBq L-1 a 54 mBq L-1 para 226Ra e 228Ra, respectivamente. O maior valor de atividade de 226Ra foi observado nas águas da Fonte Engarrafada São Jorge, enquanto que a concentração máxima de 228Ra foi determinada na Fonte Santa Filomena (torneira pública 2). As razões de atividade 228Ra/ 226Ra variaram de 1,2 (Fonte Engarrafada São Jorge) a 9,1 (Fonte Engarrafada Jatobá 1). A exposição de indivíduos do público à radiação natural em virtude do consumo das águas minerais também foi avaliada neste trabalho. As doses efetivas foram estimadas utilizando-se um modelo dosimétrico conservativo, e integrando-se os resultados ao longo de 70 anos de vida de um indivíduo adulto, após a incorporação de 226Ra e 228Ra. Os resultados desta avaliação radiossanitária demonstraram que o nível de referência de dose efetiva comprometida recomendado pela Organização Mundial de Saúde de 0,1 mSv a-1 foi ultrapassado em quase todas as fontes de Caxambu, exceto para a Fonte Viotti, Fonte Dom Pedro e Fonte Dona Leopoldina. Em Águas de Lindóia e Lindóia as maiores doses efetivas comprometidas obtidas foram 8,4 10-3 mSv a-1 para o 226Ra (Fonte engarrafada São Jorge) e 2,6 10-2 mSv a-1 para o 228Ra (Fonte Santa Filomena torneira pública 2). Estes valores são menores que o limite recomendado pela Organização Mundial de Saúde. Doses efetivas comprometidas de até 7,4 x 10-1 mSv a-1 para o 226Ra (Fonte Venâncio, Caxambu) e 2,2 mSv a-1 para o 228Ra (Fonte Ernestina Guedes, Caxambu) foram estimadas no presente trabalho. No caso do 226Ra, este valor representa menos que 31% da dose efetiva média anual atribuída a radioatividade natural. Contudo, no caso do 228Ra, o limite anual de dose efetiva comprometida recomendado pela ICRP (considerando-se todas as fontes de exposição da população mundial à radiação) foi excedido não só na Fonte Ernestina Guedes, mas também na Fonte Beleza. / The aim of this work was to study the long-lived Ra isotopes, 226Ra and 228Ra, natural distribution in mineral and spring waters from Caxambu (MG) and Águas de Lindóia (SP) waterparks. In Caxambu mineral waters it was observed 228Ra acitivity concentrations slightly higher than those of 226Ra. The elevated content of carbonates and bicarbonates of these waters can result in an increased solubility of the both Ra isotopes and may play an important role for the fate of 228Ra and its equilibrium distribution between solid and liquid phases. In Caxambu Thermal Spa, arithmetic mean activities ranged from 83 mBq L-1 to 3599 mBq L-1 and from 60 mBq L-1 to 4481 mBq L-1 for 226Ra and 228Ra, respectively. The highest 226Ra activity was found in Venancio Spring, while the maximum 228Ra activity value was determined in Ernestina Guedes. 228Ra/ 226Ra activity ratios varied from 0.079 (Conde DEau and Princesa Isabel Spring) to 4.2 (Mairink II Spring). In Águas de Lindóia, arithmetic mean activities ranged from 4.6 mBq L-1 to 41 mBq L-1 and from 30 mBq L-1 to 54 mBq L-1 for 226Ra and 228Ra, respectively. The maximum 226Ra activity concentration was found in the bottled mineral water São Jorge, while the higher 228Ra activity concentration was determined in Santa Filomena Spring (public station 2). 228Ra/ 226Ra activity ratios varied from 1.2 (bottled mineral water São Jorge) to 9.1 (bottled mineral water Jatobá 1). This work also performed the dose assessment due to the ingestion of 226Ra and 228Ra in Caxambu and Águas de Lindóia mineral and spring waters. The committed effective doses were estimated by using a conservative dosimetric model and taking into account the results over a lifetime (70 years) following intake of both long-lived Ra isotopes. The results from this radiological evaluation showed that the guindance committed effective dose level of 0.1 mSv y-1 recommended by World Health Organization was exceeded in almost all samples studied in Caxambu, except for Viotti Spring, Dom Pedro Spring and Dona Leopoldina Spring. In Águas de Lindóia and Lindóia, the highest committed effective doses estimated were 8.4 10-3 mSv y-1 for the intake of 226Ra (bottled mineral water São Jorge) and 2.6 10-2 mSv y-1 for 226Ra (Santa Filomena spring station 2). Both values are below the limit recommended by World Health Organization. The maximum commited effective doses per year obtained in this work were 7.4 10-1 mSv y-1 for 226Ra (Venancio Spring) and 2.2 mSv y-1 for 228Ra (Ernestina Guedes Spring). Considering the case of 226Ra intake via mineral water, the dose obtained represents less than 31 % of the average effective dose attributable annually from natural background radiation. However, in the case of 228Ra the annual committed effective dose limit recommended by ICRP (considering all sources of radiation exposure for the world population) was exceeded not only in Ernestina Guedes Spring, but also in Beleza Spring.

As atividades específicas do 238U, 226Ra, 210Pb, 232Th e 40K, foram medidas, utilizando-se a técnica de espectrometria gama de alta resolução, em amostras de solo coletadas em três furos com 2,10 m de profundidade e feitos com trado manual. O material amostrado é um latossolo desenvolvido sobre rochas quartzo-feldspáticas. O local da amostragem, no terreno do Instituto de Botânica da Secretaria do Meio Ambiente do Estado de São Paulo, possui uma cobertura vegetal densa que, junto com a camada superficial de solo, não é perturbada desde, pelo menos, 1938. Os 0,60 m superior da camada de solo amostrada correspondem aos horizontes O e A, enquanto que os 1,50 m restantes correspondem ao horizonte B. As medidas de atividade específica do 210Pb foram corrigidas para compensar os efeitos da absorção da radiação gama com 46,5 keV pela matriz de solo. O procedimento de correção baseado na literatura disponível, foi adaptado com o desenvolvimento de equações apropriadas para representar a geometria de detecção em que as medidas foram realizadas. Os resultados mostram que as atividades específicas do 238U e do 226Ra variam pouco em função da profundidade. O perfil de atividades do 238U parece refletir a distribuição dos minerais de argila no perfil de solo, enquanto que o perfil de atividades do 226Ra apresenta um valor praticamente constante em todo o solo analisado. O perfil de atividades do 210Pb mostra um leve enriquecimento desse isótopo nos horizontes O e A em relação ao restante do perfil. Com a exceção dos horizontes mais superficiais, o 226Ra está em desequilíbrio radioativo com o 238U e o solo apresenta razões de atividade 226Ra/238U da ordem de 0,90. O 210Pb está em desequilíbrio radioativo com o 226Ra sendo que as razões de atividade 210Pb/226Ra variam em torno de 0,7 na maior parte do perfil. A atividade específica do 210Pb é inferior à atividade específica do 226Ra em valores que variam de 8 Bq/kg a 18 Bq/kg. A série do 232Th está em equilíbrio radioativo secular em todas as amostras analisadas. As atividades específicas mais baixas do 232Th são observadas nos horizontes O e A. O horizonte B é enriquecido em 232Th o que reflete a maior concentração de argilas nesse horizonte. O 40K está distribuído de forma irregular ao longo do perfil de solo analisado e apresenta atividades específicas variando desde valores abaixo do limite de detecção do laboratório até 37,8 Bq/kg. / The specific activities of 238U , 226Ra, 210Pb, 232Th and 40K were measured, and the 226Ra/238U and 210Pb/226Ra activity ratios were calculated for samples collected in a 2.10 m deep soil profile in a preserved area of the São Paulo Botanic Garden. The sampling site is covered by dense vegetation that, together with the upper soil layer, has not been disturbed since, al least, 1938. The upper 0.60 m of the soil profile corresponds to the O and A soil horizons, whereas the remaining 1.50 m of the profile corresponds to the B horizon. The 210Pb specific activity measurements were corrected for the attenuation of the 46.5 keV gamma radiation by the soil mineral matrix. The attenuation correction procedure is based on the available literature and was adapted to represent the detection geometry of the measurements. The results show that the uranium series is in radioactive disequilibrium in most of the sampled soil. The 226Ra/238U activity ratios vary around 0.9 whereas the 210Pb/226Ra activity ratios resulted in a mean value of 0.7. The unsupported 210Pb specific activities are between -8 Bq/kg and -18 Bq/kg. The 232Th series is in secular radioactive equilibrium in the whole sampled soil layer. The 232Th specific activity distribution seems to reflect the concentration of clay minerals in the soil horizon B. The 40K radionuclide is irregulary distributed in the whole sampled soil layer and it?s specific activities varying from below detection limit to about 37.8 Bq/kg.

Une campagne d'échantillonnage de fluides a été effectuée en 2008 et 2009 dans le champ géothermique de Los Azufres, qui se trouve dans la Ceinture Volcanique Transmexicaine, afin de développer de nouveaux outils géochimiques pour tracer l'évolution de ces fluides qui sont exploités pour la production d'énergie électrique. Lors de ces campagnes, une carotte de dépôts hydrothermaux a été prélevée dans le secteur de thermes de Maritaro (Los Azufres) où les phénomènes hydrothermaux à la surface (fumerolles, volcans de boue, etc.) sont les plus actifs. Le but de cette étude était de dater ces évènements hydrothermaux par le moyen des chronomètres 226Ra, 228Ra et 210Pb, en utilisant la méthode développée par Condomines et al. (1999). Pour déterminer les possibles sites minéraux où le radium pourrait se concentrer, la minéralogie et la chimie de la carotte ont été examinées par diffraction des rayons X et par fluorescence des rayons X. Les résultats ont montré la présence de minéraux secondaires comme les argiles (kaolinite) et les sulfates hydratés de potassium (alunite) qui sont des produits d'altération de roches volcaniques par les eaux thermales acides. Les concentrations du radium (226Ra de 0.502 à 1.514 dpm/g, 228Ra de 0.077 à 1.302 dpm/g) et du plomb (210Pb de 0.204 à 0.734 dpm/g) mesurés dans les sédiments montrent une forte diminution par rapport aux teneurs mesurées dans les fluides du champ géothermique de Los Azufres (226Ra de 0.1688 à 3.0989 dpm/g). D'autre part, les ratios 228Ra/226Ra et 210Pb/226Ra s'approchent de l'équilibre séculaire. Cette absence de radium peut être expliquée par l'inhibition de l'adsorption du radium sur les argiles et les sulfates dans un environnent fortement acide avec un pH ≤ 3. Néanmoins, en appliquant des modèles chronologiques simples nous pouvons estimer des âges maximaux de 20 à 50 ans de la mise en place des dépôts hydrothermaux superficiels du secteur de Maritaro, démontrant une activité hydrothermale intense. ______________________________________________________________________________ MOTS-CLÉS DE L’AUTEUR : radium, dépôts hydrothermale, Los Azufres, Maritaro, fluides hydrothermales

<p>Groundwater has an important role in forging the composition of surface water, supplying nutrients crucial for the development of balanced ecosystems and potentially introducing contaminants into otherwise pristine surface water. Due to water-rock interactions radium (Ra) in groundwater is typically much more abundant than in surface water. In saline environments Ra is soluble and is considered a conservative tracer (apart for radioactive decay) for Ra-rich groundwater seepage. Hence in coastal environments, where mostly fresh groundwater seep into saline surface water, Ra has been the prominent tracer for tracking and modeling groundwater seepage over more than three decades. However, due to its reactivity and non-conservative behavior, Ra is rarely used for tracing groundwater seepage into fresh or hypersaline surface water; in freshwater, Ra is lost mostly through adsorption onto sediments and suspended particles; in hypersaline environments Ra can be removed through co-precipitation, most notably with sulfate salts. </p><p>This work examines the use of Ra as a tracer for groundwater seepage into freshwater lakes and rivers and into hypersaline lakes. The study examines groundwater-surface water interactions in four different environments and salinity ranges that include (1) saline groundwater discharge into a fresh water lake (the Sea of Galilee, Israel); (2) modification of pore water transitioning from saline to freshwater along their flow through sediments (pore water in sediments underlying the Sea of Galilee, Israel); (3) fresh groundwater discharge into hypersaline lakes (Sand Hills, Nebraska); and (4) fresh groundwater discharge into a fresh water river (Neuse River, North Carolina). In addition to measurement of the four Ra isotopes (<super>226</super>Ra, <super>228</super>Ra, <super>223</super>Ra, <super>224</super>Ra), this study integrates geochemical (major and trace elements) with additional isotopic tools (strontium and boron isotopes) to better understand the geochemistry associated with the seepage process. To better understand the critical role of salinity on Ra adsorption, this study includes a series of adsorption experiments. The results of these experiments show that Ra loss through adsorption decreases with increasing salinity, and diminishes in salinity as low as ~5% of the salinity of seawater. </p><p>Integration of the geochemical data with mass-balance models corrected for adsorption allows estimating groundwater seepage into the Sea of Galilee (Israel) and the Neuse River (North Carolina). A study of the pore water underlying the Sea of Galilee shows significant modifications to the geochemistry and Ra activity of the saline pore water percolating through the sediments underlying the lake. In high salinity environments such as the saline lakes of the Nebraska Sand Hills, Ra is shown to be removed through co-precipitation with sulfate minerals, its integration into barite (BaSO₄) is shown to be limited by the ratio of Ra:Ba in the precipitating barite. </p><p>Overall, this work demonstrates that Ra is a sensitive tracer for quantifying groundwater discharge even in low-saline environments. Yet the high reactivity of Ra (adsorption, co-precipitation, production of the short-lived isotopes) requires a deep understanding of the geochemical processes that shape and control Ra abundances in water resources.</p> / Dissertation