Teores anômalos de cromo hexavalente vêm sendo detectados na água subterrânea de vários municípios da região noroeste do Estado de São Paulo, sendo que em Urânia foram observadas as maiores concentrações do elemento, afetando as condições do consumo e uso humano. Estudos prévios realizados indicaram que a origem do cromo na água subterrânea é natural e proveniente de minerais com cromo no aqüífero profundo. Este projeto teve como principais objetivos: (1) a caracterização química e mineralógica da fase sólida do aqüífero profundo, realizada em testemunhos de duas sondagens profundas; (2) a caracterização da estratificação das concentrações de cromo na água subterrânea, com base na coleta e análise de amostras de água provenientes de poços de monitoramento instalados em diferentes profundidades do aqüífero; (3) a identificação dos processos hidrogeoquímicos que justificam a passagem do cromo da fase sólida para a água. Para tanto, foram realizadas análises químicas e mineralógicas por WDS, microssonda eletrônica e CTC, diversos métodos de análise química da água subterrânea, utilizados programas como o AquaChem e PHREEQc para trabalhamento do banco de dados e modelagens, além de uma grande variedade de experimentos de laboratório. As análises químicas por WDS e microssonda eletrônica indicaram concentrações de cromo de até 12.600 ppm em cristais de diopsídio, e de 650 ppm em capas de argilomineral. O material sólido apresenta uma capacidade de troca de cátions da ordem de 30 meq/100g, com ordem de abundância dos cátions Ca>>Mg>>K>Na. Na porção profunda do aqüífero, foi observada uma anomalia de sódio adsorvido, influenciando na composição química da água. As características hidroquímicas do aqüífero indicaram a ocorrência de estratificações de águas com diferentes perfis hidroquímicos. As águas são, no geral, do tipo bicarbonatadas cálcicas, porém com uma elevação do conteúdo de sódio na base do aqüífero. O cromo foi identificado na água predominantemente na forma hexavalente, com concentrações que atingiram 0,139 mg/L, acima, portanto do limite de potabilidade (0,05 mg/L). A ocorrência de valores mais elevados de cromo na água parece estar associada a ambientes de elevados pH e Eh, como observado no aqüífero profundo, enquanto que nas zonas rasas, que apresentam valores de pH e Eh neutros, apresentaram baixo conteúdo de cromo. Os principais resultados dos ensaios de laboratório indicaram que há passagem de cromo para água subterrânea, através do ataque aos minerais pesados com pH ácido; os ensaios de batch test realizados apontaram que o material sólido do aqüífero apresenta alguma capacidade de adsorção de Cr6+, chegando a um máximo de 0,12 ppm; o experimento de solubilização indicou a passagem de pequenas concentrações de cromo para a água e que a composição química da água do ensaio é semelhante à água do aqüífero. O modelo mais provável das reações geoquímicas que explicam a passagem do cromo da fase sólida para a água é apresentado a seguir, divido por etapas: (1) o intemperismo dos diopsídios cromíferos deve ser o processo inicial de disponibilização de cromo para a água, resultando na precipitação do cromo como hidróxidos ou sendo adsorvido por hidróxidos de ferro e manganês; (2) ocorrência de uma reação de oxi-redução a partir do cromo trivalente que ocorre nos minerais secundários, disponibilizando o cromo para a água subterrânea, sendo que esta oxidação ocorre a partir da redução de óxidos de manganês presentes como minerais em aqüíferos, liberando Mn2+; (3) O Cr3+ é rapidamente e fortemente imobilizado por adsorção em argilominerais de baixo valor de pHpzc, enquanto que o Cr6+, devido à sua natureza aniônica, é preferencialmente retido em superfícies carregadas positivamente, como os óxidos e hidróxidos de ferro e alumínio (minerais com elevados valores de pHpzc), principalmente em condições hidroquímicas neutras a ácidas; (4) altas concentrações de OH-, de HCO3- e de CO3 2- provavelmente elevam a competição pelos sítios de adsorção de ânions e causam a dessorção dos ânions de Cr6+ para a água do aqüífero. / Anomalous hexavalent chromium contents have been detected in groundwater in many municipalities of the northwestern region of São Paulo state. In the city of Urânia, the highest concentrations of this element have been observed, affecting the conditions for human consumption. Previous studies indicated that the origin of chromium in groundwater is from natural sources and derived from chromium minerals in the deep aquifer. The main objectives of this research are to: (1) characterize chemically and mineralogically the solid phase from the deep aquifer; (2) characterize the stratification of chromium concentrations in groundwater, based on sampling and analysis of groundwater from wells installed in different depths of the aquifer; (3) identify hydrogeochemical processes that justify the passage of chromium from solid phase to groundwater. To achieve these objectives, chemical and mineralogical analysis by WDS, microprobe and CEC were made, diverse chemical analytical methods were used for groundwater, database and modeling were used through AquaChem and PHREEQc programs, besides a great variety of laboratory experiments. Chemical analysis from WDS and microprobe indicated chromium concentrations of up to 12.600 ppm in diopside crystals, and up to 650 ppm in clay mineral coats. The solid material has a Cation Exchange Capacity (CEC) of about 30 meq/100g, with cation abundance order of Ca>>Mg>>K>Na. In the aquifer deep zone, it was observed an adsorbed sodium anomaly, that influences groundwater chemical composition. The aquifer hydrochemical characteristics indicated the occurrence of water stratifications with different hydrochemical profiles. The groundwaters are, in general, calcium bicarbonated, with a elevation of sodium contents in the base of the aquifer. Chromium was identified predominatly in hexavalent state of oxidation, with concentrations of up to 0,139 mg/L, thus above potability standards (0,05 mg/L). The occurrence of higher chromium concentrations in groundwater seems to be related to high pH and Eh environments, whereas shallow zones, that have neutral values of pH and Eh, presented low chromium contents. The main results of laboratory experiments have indicated that there is passage of chromium to groundwater through acid etching in heavy minerals; batch tests have shown that solid phase has some sorption capacity, reaching a maximum of 0,12 ppm; solubilization experiment indicated the passage of low concentrations of chromium to water and that chemical composition from the experiment water is similar to groundwater. The probable model that explain the passage of chromium from solid phase to groundwater is presented hereafter, divided in steps: (1) it is indicated that weathering of chromium diopsides must be the initial process of availability of chromium to water; (2) hexavalent chromium can only occur in groundwater after the occurrence of an oxi-reduction reaction from the trivalent chromium that occurs in minerals. Many authors recognize that this oxidation occurs from the reduction of manganese oxide presented as minerals in the aquifer, releasing Mn2+, that later will be oxidated again; (3) the trivalent chromium is rapidly and strongly immobilized by sorption in clay minerals of low values of pHzpc, whereas the hexavalent chromium, due to its anionic nature, is preferably retained in positively charged surfaces, like iron and aluminium hydroxides (minerals with high values of pHzpc), mainly in neutral to acid hydrochemical conditions; (4) high OH-, HCO3 - and CO3 2- concentrations probably elevate the competition for anion sorption sites and cause the desorption of hexavalent chromium anions to groundwater.

Natural attenuation of trichloroethene (TCE) and technetium (99Tc) was studied for five consecutive seasons (from January 2002 to January 2003) in Little Bayou Creek. The stream receives ground water discharge from an aquifer contaminated by past waste disposal activities at the Paducah Gaseous Diffusion Plant (PGDP), a uranium enrichment facility near Paducah, Kentucky. Results from stream gaging, contaminant monitoring, tracer tests (with bromide, nitrate, rhodamine WT and propane) and simulation modeling indicate the TCE is naturally attenuated by volatilization and dilution, with volatilization rates related to the ambient temperature and surface discharge rate. The only apparent mechanism of 99Tc attenuation is dilution. Travel times of non-gaseous tracers were found to be similar and have highest values in October and lowest in June. It was also estimated from modeling that the transport of the solutes in the stream was mostly one-dimensional with insignificant secondary storage.

Despite being one of the largest aquifers of its type in Australia, the Burdekin River Delta (BRD) is an area that has received comparatively little research on its groundwater resources. This study conceptualises the hydrogeology of the BRD and characterises the relationships between the stratigraphic elements and the physical and chemical components of the groundwater system that influence the major governing processes. Importantly, a large amount of spatial and temporal groundwater information exists in database form, which enables an integrated conceptual model of the BRD aquifer to be developed from the key hydrogeological and hydrogeochemical relationships. Conceptualisation of the BRD aquifer is achieved by categorising four main aspects of the groundwater resource: 1. Surface characterisation; 2. Geologic characterisation; 3. Hydrogeologic characterisation; and 4. Groundwater System characterisation. The BRD is a large cuspate delta comprising a complex stratigraphy of Pleistocene to Holocene sediments of fluvial, deltaic and marine origin to a maximum depth of about 150 metres. The lower Pleistocene sediments lie predominantly below sea level and are typified by laterally discontinuous sands, silts and clays that have formed in response to fluctuating sea levels. The upper Pleistocene boundary is differentiated from the overlying Holocene sediments by a formerly exposed surface of semiconsolidated oxidised sandy clays and gravel. By contrast, the Holocene sediments comprise loose, uncompacted sequences of fluvial channel sands, interdistributary floodplain silts and marine incursions of estuarine clays and mangrove muds. The anastomosing array of fluvial sand bodies of former Burdekin River channels and levees is the setting for the main shallow aquifer units. Aquifer units of the lower Pleistocene sediments are in hydraulic connection with the Holocene units, effectively categorising the whole BRD as a single unconfined aquifer. Hydraulic gradients from both sides of the river divide the BRD into two broad flow regimes. Interpreted flow zones based on hydrograph patterns further subdivide the flow system based on seasonal recharge response to elevated river heights and flooding, and response to long-term rainfall patterns associated with La Niña episodes of the Southern Oscillation. Stable isotope data (2H and 18O) indicate that the dominant isotopic signature of groundwater throughout the BRD corresponds with intense rainfall activity, however high deuterium-excess values indicate that significant evaporation occurs prior to recharge. This infers dominant recharge by the Burdekin River that drains a massive catchment extending hundreds of kilometres inland. Direct recharge via rainfall infiltration is largely dependant on soil texture. More conductive soils are associated with the major levee systems that comprise the main shallow aquifers. Two evolutionary hydrogeochemical paths exist for the north and south sides of the river, and are constrained by the interpreted flow zones. In the south side, groundwater enters the main aquifer from river recharge and leakage out of weathered granite outcrops (exposed bedrock). Mineral hydrolysis and evaporative concentration of salts initially evolve groundwater in the weathered granite to a combination of Na-Cl and Na-HCO3 type. Leakage through clay-rich hillwash and marginal sediments causes reverse cation-exchange reactions where excess Na replaces Ca and Mg on ion-exchange surfaces. This leads to the formation of Mg,Ca-Cl type groundwaters into the southern parts of the main aquifer (supersaturated with respect to calcite and dolomite). Discharge towards the coast is characterised by seawater mixing where salinity increases with corresponding evolution to Na-Cl type waters. Recharge waters from the Burdekin River are fresh (<250mS/cm) Ca-HCO3 type, undersaturated with respect to calcite, and are easily distinguishable from the ion-exchange groundwater. In the north, only one smaller outcrop of bedrock exists, which hosts similar mineral hydrolysis reactions and base-exchange reactions. An absence of associated Na-Cl type waters means that reverse-cation exchange reactions are negligible, and so water types are predominantly Na-HCO3 type. Aquifer sands in the north are more widespread than in the south, so the fresh Ca-HCO3 recharge waters tend to dominate the overall groundwater composition, with Na-HCO3 types limited to the exposed bedrock areas. Towards the coastline, groundwater mixes with seawater towards Na-Cl type waters, similar to that observed in the south. The mangrove mud sequences that flank the coastline of the BRD are associated with high-Fe and low-pH groundwater formed by the oxidation of Fe-sulphides such as pyrite). SO4 is a product of this reaction, but does not achieve abnormally high concentrations, possibly due to the presence of sulphate-reducing bacteria. Carbonate dissolution is a possible side effect of acid sulphate generation, with possible gypsum dissolution as a secondary source of SO4. This study tested an alternative method to characterising groundwater to determine if the spatial extent of hydrogeochemical processes could be defined and comparable results achieved. This method involved discriminating discrete statistical groups of ionic ratios based on their cumulative frequency distribution. The statistical groups are bounded by critical values that distinguish different chemical processes, referred to as hydrogeochemical indicators. Various tested ionic ratios produced analogous indicators, proving their reliability as a valid method for the characterisation of groundwater chemistry. The significance of this research underlies the importance of groundwater use in the BRD as a primary source of irrigation supplies. Land use expansion and unregulated pumping pose a risk to future groundwater quality and sustainable volumes. The understanding of the relationship between the main geologic elements and the subsequent hydrogeochemical processes provides a scientific basis for conceptualising the groundwater resource. This establishes a framework for initiating future groundwater management options.

CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior / Esse trabalho foi realizado no municÃpio de Fortaleza, localizado na zona litorÃnea da porÃÃo nordeste do Estado do CearÃ, RegiÃo Nordeste do Brasil, abrangendo 314,8 km e com 2.452,18 habitantes, objetivando analisar a situaÃÃo qualitativa das Ãguas subterrÃneas de Fortaleza, Cearà â Brasil como subsÃdio à GestÃo dos Recursos HÃdricos. Foram coletadas 120 amostras de Ãgua subterrÃnea para anÃlises fÃsico-quÃmicas, complementadas com 171 anÃlises realizadas entre 2001 a 2009 (Arquivo de dados do LaboratÃrio de Hidrogeologia/UFC). Os dados foram tratados com anÃlise estatÃstica, correlaÃÃo, identificaÃÃo do ambiente de deposiÃÃo, relaÃÃes iÃnicas, classificaÃÃo iÃnica e o enquadramento das Ãguas na Portaria N 2914/2011 do MinistÃrio da SaÃde. Com estes dados conclui-se que Ãrea à caracterizada por um ambiente redutor e Ãcido/bÃsico, com Eh no intervalo de -0,1 V e 0,2 V e de pH entre 4 e 9; as relaÃÃes iÃnicas rMg+2/rCa+2 e rK+/rNa+, estÃo associadas à silicatos magnesianos e a fixaÃÃo de K+ nos argilominerais, respectivamente. Predominam Ãguas Cloretadas (86% e 81%) e SÃdicas (67% e 77%). Das 87 anÃlises bacteriolÃgicas, 77% dessas mostraram a presenÃa de coliformes totais e/ou fecais. A classe das Ãguas para a irrigaÃÃo que predomina à C2 - S1 (49 e 73,5%), indicando um mÃdio risco de salinidade e baixo risco de sÃdio, podendo ser utilizadas para irrigaÃÃo em grande parte dos solos e plantas com tolerÃncia salina. As potenciais fontes de poluiÃÃo identificadas na Ãrea foram a construÃÃo de poÃos tubulares sem adotar-se as normas tÃcnicas da ABNT, cemitÃrios, lixÃes inativos, posto de combustÃveis, infiltraÃÃo de Ãguas superficiais contaminadas e ausÃncia de saneamento bÃsico em bairros de Fortaleza. As inundaÃÃes em Fortaleza resultam da alteraÃÃo do uso do solo e ocupaÃÃo dos ambientes fluviais e lacustres, que aliado Ãs chuvas mais intensas e concentradas da quadra chuvosa, bem como ao nÃo acompanhamento do crescimento de infraestruturas e equipamentos de drenagem no mesmo ritmo do crescimento da cidade, gera problemas desta natureza. Para a inserÃÃo formal dos aspectos qualitativos das Ãguas subterrÃneas no vetor gestÃo dos recursos hÃdricos, deve se ter como base os fundamentos de LegislaÃÃo EspecÃfica, Programa de EducaÃÃo Ambiental, CaracterizaÃÃo das Bacias HidrogrÃficas, Cadastramento e diagnÃstico dos poÃos e por fim o gerenciamento das Ãguas. / This work was conducted in the city of Fortaleza, located in the coastal zone of the northeastern portion of the state of CearÃ, northeastern Brazil, covering 314,8 km and 2.452,18 inhabitants, aimed to analyze the qualitative groundwater in Fortaleza, Cearà - Brazil as a subsidy to Water Resources Management. We collected 120 groundwater samples for physico-chemical analyzes, supplemented with 171 analyzes conducted between 2001-2009 (Data File Hydrogeology Laboratory / UFC). The data were processed with statistical analysis, correlation, identification of depositional environment, ionic relations, classification and framing of ionic water in Ordinance No. 2914/2011 of the Ministry of Health With these data it is concluded that the area is characterized by a reducing environment and acidic / basic with Eh in the range of -0,1 V to 0,2 V and pH between 4 and 9, the relationships ionic rMg+2/rCa+2 and rK+/rNa+, are associated with magnesia silicates and fixation K+ in clay, respectively. Chlorinated water predominate (86% and 81%) and Sodic (67% and 77%). Bacteriological analyzes of 87, 77% of these showed the presence of total coliform and / or fecal. The class of waters for irrigation is predominant C2 - S1 (49 and 73,5%), indicating salinity medium risk and low risk sodium, may be used largely for irrigation of soil and plants salt tolerance. The potential pollution sources identified in the area were building wells without taking up the technical standards of ABNT, cemeteries, inactive dumps, gas station, infiltration of contaminated surface water and lack of basic sanitation in neighborhoods of Fortaleza. Floods in Fortaleza result of the change of land use and occupation of fluvial and lacustrine environments, which coupled with the heaviest rains of the rainy season and concentrated, and not follow the growth of infrastructure and equipment drain at the same rate of growth of city, creates problems of this nature. For the formal insertion of the qualitative aspects of groundwater in vector management of water resources should be based on the fundamentals of Specific Legislation, Environmental Education Program, Watershed Characterization, Registration and diagnosis of wells and finally the management of water .

Teores anômalos de cromo hexavalente vêm sendo detectados na água subterrânea de vários municípios da região noroeste do Estado de São Paulo, sendo que em Urânia foram observadas as maiores concentrações do elemento, afetando as condições do consumo e uso humano. Estudos prévios realizados indicaram que a origem do cromo na água subterrânea é natural e proveniente de minerais com cromo no aqüífero profundo. Este projeto teve como principais objetivos: (1) a caracterização química e mineralógica da fase sólida do aqüífero profundo, realizada em testemunhos de duas sondagens profundas; (2) a caracterização da estratificação das concentrações de cromo na água subterrânea, com base na coleta e análise de amostras de água provenientes de poços de monitoramento instalados em diferentes profundidades do aqüífero; (3) a identificação dos processos hidrogeoquímicos que justificam a passagem do cromo da fase sólida para a água. Para tanto, foram realizadas análises químicas e mineralógicas por WDS, microssonda eletrônica e CTC, diversos métodos de análise química da água subterrânea, utilizados programas como o AquaChem e PHREEQc para trabalhamento do banco de dados e modelagens, além de uma grande variedade de experimentos de laboratório. As análises químicas por WDS e microssonda eletrônica indicaram concentrações de cromo de até 12.600 ppm em cristais de diopsídio, e de 650 ppm em capas de argilomineral. O material sólido apresenta uma capacidade de troca de cátions da ordem de 30 meq/100g, com ordem de abundância dos cátions Ca>>Mg>>K>Na. Na porção profunda do aqüífero, foi observada uma anomalia de sódio adsorvido, influenciando na composição química da água. As características hidroquímicas do aqüífero indicaram a ocorrência de estratificações de águas com diferentes perfis hidroquímicos. As águas são, no geral, do tipo bicarbonatadas cálcicas, porém com uma elevação do conteúdo de sódio na base do aqüífero. O cromo foi identificado na água predominantemente na forma hexavalente, com concentrações que atingiram 0,139 mg/L, acima, portanto do limite de potabilidade (0,05 mg/L). A ocorrência de valores mais elevados de cromo na água parece estar associada a ambientes de elevados pH e Eh, como observado no aqüífero profundo, enquanto que nas zonas rasas, que apresentam valores de pH e Eh neutros, apresentaram baixo conteúdo de cromo. Os principais resultados dos ensaios de laboratório indicaram que há passagem de cromo para água subterrânea, através do ataque aos minerais pesados com pH ácido; os ensaios de batch test realizados apontaram que o material sólido do aqüífero apresenta alguma capacidade de adsorção de Cr6+, chegando a um máximo de 0,12 ppm; o experimento de solubilização indicou a passagem de pequenas concentrações de cromo para a água e que a composição química da água do ensaio é semelhante à água do aqüífero. O modelo mais provável das reações geoquímicas que explicam a passagem do cromo da fase sólida para a água é apresentado a seguir, divido por etapas: (1) o intemperismo dos diopsídios cromíferos deve ser o processo inicial de disponibilização de cromo para a água, resultando na precipitação do cromo como hidróxidos ou sendo adsorvido por hidróxidos de ferro e manganês; (2) ocorrência de uma reação de oxi-redução a partir do cromo trivalente que ocorre nos minerais secundários, disponibilizando o cromo para a água subterrânea, sendo que esta oxidação ocorre a partir da redução de óxidos de manganês presentes como minerais em aqüíferos, liberando Mn2+; (3) O Cr3+ é rapidamente e fortemente imobilizado por adsorção em argilominerais de baixo valor de pHpzc, enquanto que o Cr6+, devido à sua natureza aniônica, é preferencialmente retido em superfícies carregadas positivamente, como os óxidos e hidróxidos de ferro e alumínio (minerais com elevados valores de pHpzc), principalmente em condições hidroquímicas neutras a ácidas; (4) altas concentrações de OH-, de HCO3- e de CO3 2- provavelmente elevam a competição pelos sítios de adsorção de ânions e causam a dessorção dos ânions de Cr6+ para a água do aqüífero. / Anomalous hexavalent chromium contents have been detected in groundwater in many municipalities of the northwestern region of São Paulo state. In the city of Urânia, the highest concentrations of this element have been observed, affecting the conditions for human consumption. Previous studies indicated that the origin of chromium in groundwater is from natural sources and derived from chromium minerals in the deep aquifer. The main objectives of this research are to: (1) characterize chemically and mineralogically the solid phase from the deep aquifer; (2) characterize the stratification of chromium concentrations in groundwater, based on sampling and analysis of groundwater from wells installed in different depths of the aquifer; (3) identify hydrogeochemical processes that justify the passage of chromium from solid phase to groundwater. To achieve these objectives, chemical and mineralogical analysis by WDS, microprobe and CEC were made, diverse chemical analytical methods were used for groundwater, database and modeling were used through AquaChem and PHREEQc programs, besides a great variety of laboratory experiments. Chemical analysis from WDS and microprobe indicated chromium concentrations of up to 12.600 ppm in diopside crystals, and up to 650 ppm in clay mineral coats. The solid material has a Cation Exchange Capacity (CEC) of about 30 meq/100g, with cation abundance order of Ca>>Mg>>K>Na. In the aquifer deep zone, it was observed an adsorbed sodium anomaly, that influences groundwater chemical composition. The aquifer hydrochemical characteristics indicated the occurrence of water stratifications with different hydrochemical profiles. The groundwaters are, in general, calcium bicarbonated, with a elevation of sodium contents in the base of the aquifer. Chromium was identified predominatly in hexavalent state of oxidation, with concentrations of up to 0,139 mg/L, thus above potability standards (0,05 mg/L). The occurrence of higher chromium concentrations in groundwater seems to be related to high pH and Eh environments, whereas shallow zones, that have neutral values of pH and Eh, presented low chromium contents. The main results of laboratory experiments have indicated that there is passage of chromium to groundwater through acid etching in heavy minerals; batch tests have shown that solid phase has some sorption capacity, reaching a maximum of 0,12 ppm; solubilization experiment indicated the passage of low concentrations of chromium to water and that chemical composition from the experiment water is similar to groundwater. The probable model that explain the passage of chromium from solid phase to groundwater is presented hereafter, divided in steps: (1) it is indicated that weathering of chromium diopsides must be the initial process of availability of chromium to water; (2) hexavalent chromium can only occur in groundwater after the occurrence of an oxi-reduction reaction from the trivalent chromium that occurs in minerals. Many authors recognize that this oxidation occurs from the reduction of manganese oxide presented as minerals in the aquifer, releasing Mn2+, that later will be oxidated again; (3) the trivalent chromium is rapidly and strongly immobilized by sorption in clay minerals of low values of pHzpc, whereas the hexavalent chromium, due to its anionic nature, is preferably retained in positively charged surfaces, like iron and aluminium hydroxides (minerals with high values of pHzpc), mainly in neutral to acid hydrochemical conditions; (4) high OH-, HCO3 - and CO3 2- concentrations probably elevate the competition for anion sorption sites and cause the desorption of hexavalent chromium anions to groundwater.

La dégradation de la qualité de l'eau, la variabilité climatique et la croissance démographique font partie des facteurs limitant la disponibilité de l'eau dans les régions semi-arides de Katari et de Lago Menor (6,350 Km2), entraînant une exploitation croissante des ressources en eaux souterraines. Cette thèse a pour but de conceptualiser le système d'écoulement souterrain à grande échelle et de détecter les sources de contamination par les nitrates dans les régions de Katari et Lago Menor.Dans cette étude, on a utilisé une approche multidisciplinaire comprenant un inventaire régional des sources d’eaux souterraines et des mesures du niveau piézométrique, des techniques d’investigation géophysique (sondages électromagnétiques à domaine temporel TDEM), la construction et l’installation de piézomètres, l’analyse chimique des ions majeurs et les isotopes de 15N-NO3 et de 18O-NO3.Les résultats ont permis d'identifier les limites de deux contextes géologiques différents (le sous-système du Piémont et la plaine lacustre), la géométrie du milieu géologique poreux du Quaternaire et les limites inférieures de l'aquifère. L’analyse régionale montre que les flux souterrains suivent le modèle classique d’écoulement basé sur la gravité. Six sous-domaines ont été identifiés possédant des propriétés hydrauliques différentes. Une grande partie de l'aquifère présente un comportement non confiné, en particulier sur le Piémont, alors qu'il reste confiné dans les zones de plaine. L'épaisseur de la portion non confinée varie de 50 à 150 mètres. Les valeurs de conductivité hydraulique pour la portion non confinée vont de 1.1E-4 à 5.0E-6 m/sec, le rendement spécifique de 0,16 à 0,20 et les valeurs de recharge vont de 118 à 382 mm/year. Tandis que pour la partie confinée, les valeurs de transmissivité se situent autour de 6.0 E-6 m2/sec avec une valeur de stockage de 1.2E-2 à 6.0E-3.En particulier, dans les hautes régions du Piémont où se trouvent les fortes pressions hydrauliques, les compositions minérales, chimiques et isotopiques montrent que la source d'eau souterraine est de bonne qualité. En revanche, dans la partie inférieure du Piémont, les nappes phréatiques moins profondes de la séquence alluvial-fluvioglaciaire-lacustre rendent cette zone plus vulnérable à la contamination. En fait, le faciès chimique et la composition isotopique du NO3 dissous ont révélé que l'origine principale de cet anion est liée aux engrais azotés vers le nord-ouest du Piémont et aux déchets humaines / animales vers le SE. De plus, les processus naturels d'atténuation du nitrate se produisent principalement dans le secteur inférieur du Piémont, lorsque les eaux souterraines se mélangent au réservoir d'origine lacustre.En revanche, les eaux souterraines s'écoulant dans les plaines présentent principalement des faciès de Na (K) -Cl mettant en évidence la présence d'évaporites. Dans cette zone, les eaux souterraines sont sujettes à la contamination, en particulier lorsque la couche d'argile est absente et dans les endroits où une connexion au Piémont est mise en évidence (canaux souterrains). La contribution des eaux souterraines au lac Titicaca actuel (baie de Cohana) semble être retardée en raison de la présence de la couche d'argile.Ce modèle conceptuel d'écoulement des eaux souterraines permet une bonne compréhension du fonctionnement de l’aquifère et fournit un guide pour la collecte future de données afin d'améliorer la robustesse d’une future modélisation numérique des flux d’eau souterrains. Toutes les informations scientifiques issues de cette recherche ont été rassemblées dans une base de données spatiales SIG pour aider les décideurs à gérer et à protéger les ressources en eaux souterraines. Ces informations scientifiques contribuent également à l'assainissement de l'environnement du lac Titicaca, une priorité nationale de l'État plurinational de Bolivie. / Water quality degradation, climate variability and population growth are among the factors that constrains water availability in the semi-arid Katari and Lago Menor region (6,350 Km^2), leading to an increasingly exploitation of groundwater resources. This thesis aims to conceptualize subsurface flow and trace nitrate contamination sources in the groundwater system within the Katari and Lago Menor Region.A multidisciplinary approach for field investigation was used in this study, including a regional groundwater source inventory and groundwater level measurements, geophysical investigation techniques (e.g. TDEM-Time Domain ElectroMagnetic soundings), piezometer construction and installation, and a regional sampling campaign and analysis for major ion chemistry and dual isotopes of 15N-NO3 and 18O-NO3.The results allowed identifying the limits of two different geological settings (Piedmont subsystem and Lacustrine plain), the geometry of the Quaternary porous geologic media and the bottom boundaries of the aquifer.The groundwater flow regime corresponds to a classical gravity-driven regional flow system. Six subdomains possessing different hydraulic properties were identified. A large portion of the aquifer presents an unconfined behaviour, particularly on the Piedmont, whereas it remains confined in the plain areas. The thickness of the unconfined portion varies from 50 to 150 meters. Values of hydraulic conductivity for the unconfined portion range from 1.1E-04 to 5.9E-08 m/sec, specific yield ranges from 0.16 to 0.20 and recharge values range from 118 to 382 mm/year. While for the confined part the transmissivity values range around 6.0E-06 m^2/sec with a storavity value of 1.2E-02 to 6.0E-03.In the high Piedmont areas where the hydraulic heads are high, the low mineralization and the chemical and isotopic compositions showed that the groundwater source is of good quality. In contrast, in the lower sector of the Piedmont, the shallower water tables of the alluvial-fluvioglacial-lacustrine sequence, make this area more vulnerable to contamination. Chemical facies and the isotopic composition of the dissolved NO3 revealed that the main origin of this anion is related to nitrogen fertilizers towards the NW of the Piedmont and human/animal waste towards the SE. Moreover, natural nitrate attenuation processes occur mainly in the lower sector of the Piedmont, when groundwater mixes with the reservoir of lacustrine origin. Groundwater flowing in the plain areas, present primarily Na(K)-Cl facies relating the presence of evaporites. In this area groundwater is prone to contamination, especially when the clay layer is absent and in places where a connection to the Piedmont is evidenced (subterranean channels). The contribution of groundwater to the current Lake Titicaca (Cohana Bay) appears to be retarded due to the presence of the clay layer.This basin-scale conceptual groundwater flow model provides a good understanding of the aquifer functioning, and a guide to future data collection, in order to improve the robustness of future groundwater flow numerical modeling. All the science-based information generated from this research was arranged into a GIS spatial database to support decision makers in the management and protection of groundwater resources. This science-based information also contributes to the environmental remediation of Lake Titicaca, a national priority for the Plurinational State of Bolivia.

Na última década foram encontradas concentrações anômalas de bário em poços de abastecimento do Sistema Aquífero Bauru (SAB), com casos de ocorrências de teores acima do limite de potabilidade (0,7 mg/L). Estas concentrações foram encontradas pelo monitoramento da CETESB e por estudos anteriores. Tavares (2013) e Crespi (2013) indicam que a contaminação nesta área tem origem natural, advinda da lixiviação da cimentação carbonática da Formação Marília. Utilizando dados bibliográficos e expandindo o estudo para toda a região do Espigão de Marília, este trabalho visou aprofundar o conhecimento sobre esta anomalia e tentar compreender o seu comportamento com auxílio de dados isotópicos (O e H) de chuva e água subterrânea. Para o entendimento da anomalia foi construído um banco de dados com os Autos de Outorga de poços do DAAEE, CETESB e CPRM. Após o cadastro destes dados, foram confeccionadas as seções geológicas, o modelo conceitual de fluxo da área, e um modelo hidrogeológico. Após esta etapa foram selecionados 21 poços para as duas primeiras campanhas de amostragem ao longo do ano hidrológico e 8 poços para uma terceira campanha de amostragens ao longo do ano hidrológico. Simultaneamente foi instalado no DAAEE de Marília um coletor de chuva para coletar amostras desde junho de 2014 até dezembro de 2015 para a confecção da reta meteórica local. Os resultados analíticos dos poços foram tratados agrupando-os de acordo com sua geologia, observando-se padrões de distribuição dos parâmetros químicos analisados, bem como dos isótopos. Foi possível notar que há contaminação por cloreto e nitrato em alguns poços. A contaminação de bário ocorre em diferentes pontos, não estando restrita a apenas uma formação. Sem nenhuma relação com os demais componentes antrópicos, esta anomalia se confirma natural. Os altos teores de bário também aparecem em locais com uma maior variedade geológica. A análise dos isótopos de hidrogênio e oxigênio das amostras mostrou que as águas amostradas são mais empobrecidas que as de chuva, até mesmo as mais rasas. Em teste de bombeamento foi possível acompanhar a evolução da assinatura com a profundidade. O que pode ser concluído é que a anomalia de bário ocorre em todo o Espigão, em geral em poços com filtros nas Formações Marília e Adamantina, que possuam um teor mais elevado de magnésio, não necessariamente tendo uma influência antrópica. / In the last decade, anomalous concentrations of barium were found in supply wells of Bauru Aquifer System (BAS), with occurrences of levels above the drinking limit (0.7 mg/L). These concentrations were found by CETESB monitoring and some previous studies. Tavares (2013) and Crespi (2013) indicate that contamination in this area has natural origin, from the leaching of carbonate cementation of Marília Formation. Using bibliographic data and expanding the study to the entire region of the Espigão de Marília this study aimed to increase knowledge about this anomaly and try to understand their behavior with aid of isotopic data (O and H) of rain and groundwater. For the understanding of the anomaly, a database was built with information from DAAEE, CETESB and CPRM wells. After the register of this database, some geological sections were made, the groundwater flow conceptual model for the area, and a geological model. After this step, 22 wells were selected for the three sampling campaigns. At the same time was installed in DAAEE of Marília a rain collector that operated from middle of 2014 by the end of 2015, to construct a Local Meteoric Water Line. The wells have been grouped according to the geology, and some patterns were discovered. It was possible to notice that there is a problem about chloride and nitrate contamination. Barium contamination appeared at various points, not being restricted to just one Formation. Without any relation with man-made components, according to the bibliography, this anomaly confirms natural. High levels of barium also appear in places with greater geological variety. The analysis of the isotopes of hydrogen and oxygen of the samples showed that the waters sampled are isotopic depleted compared to the rain. In pumping test was possible to monitor the evolution of the signature with the depth. It is possible to conclude that the barium anomaly is spread all over the Espigão de Marília, in general in wells with filters in Marília and Adamantina Formations, which have a higher content of magnesium, not necessarily having a human influence.

Este projeto visou quantificar e determinar a origem da recarga do aquífero freático na zona urbana do município de Urânia (SP). A área está localizada no extremo noroeste do Estado de São Paulo, sobre sedimentos arenosos da Formação Vale do Rio do Peixe, do Grupo Bauru. A metodologia usada foi de balanço hídrico e variação de nível de água para a quantificação da recarga e técnicas hidroquímicas e isotópicas para o estudo de origem da água. Foram analisadas águas da chuva, poços cacimbas, poços tubulares, poços que exploram o Aquífero Bauru e Sistema Aquífero Guarani, esgoto e água distribuída pela SABESP. O clima na região é dividido em duas estações: a úmida, de outubro a maio, e a seca, de junho a setembro. A precipitação acumulada, entre setembro de 2007 e agosto de 2008, foi de 2498 mm. Pelo método do balanço hídrico, 10% deste total (247 mm) correspondem ao escoamento superficial, 69% (1734 mm) voltam diretamente à atmosfera por evapotranspiração, restando 21% (517 mm) para recarga. Através do método de variação do nível d´água, monitorado em dois poços de profundidades distintas, foi calculada a recarga para o período de setembro de 2008 a abril de 2010. O volume de precipitação registrado foi de 2742 mm, e a recarga calculada somou 20% deste total (544 mm) para o poço mais raso, e 16% (456 mm) para o mais profundo. Os dados de nível de água mostraram também que apenas chuvas maiores de 100 mm por mês são capazes de elevar os níveis de água. Através da coleta de amostras mensais de chuva para análises de isótopos estáveis de oxigênio e hidrogênio foi determinada a reta meteórica local (D = 8,5 18O + 17 ( VSMOW)). Através dos isótopos estáveis de oxigênio e hidrogênio foi possível definir que a recarga da água subterrânea é predominantemente proveniente da água de chuva, podendo ter contribuição pequeno proveniente de vazamentos da rede de água da SABESP e do esgoto. Os isótopos radiogênicos de chumbo não mostraram nenhum resultado significativo para o estudo de origem da água subterrânea. Os resultados dos isótopos radiogênicos de estrôncio e de hidroquímica indicaram a existência de um zoneamento do aquífero, que pode ser dividido em raso, intermediário e profundo. Isto possibilita a identificação da contribuição de cada zona para os poços tubulares. A maioria das amostras apresentou contribuição menor do que 8% da água classificada hidroquimicamente e isotopicamente como rasa, e o restante de água profunda. Porém a contribuição pode chegar a 49% de água rasa, indicando alta vulnerabilidade à contaminação. Portanto, os isótopos de estrôncio tem potencial para ser uma ferramenta importante em estudos de vulnerabilidade e gestão de águas subterrâneas. / The focus of this project is to identify the source and quantify the recharge of the unconfined portion of the Bauru aquifer, present in the urban area of Urania, a small city located at the northwestern corner of São Paulo State, Brazil. The aquifer is composed by sandy sediments of the Vale do Rio do Peixe Formation, Bauru Group. Water balance and water table fluctuation were used to quantify the recharge. Hydrochemistry and isotopes, both stable and radioactive, were used to determine recharge sources. Rain water samples were collected, as well as from shallow and deep wells taping the Bauru aquifer and the confined Guarani Aquifer System (GAS), and from the public water supply system, which is a mixture of both aquifers. Climate is tropical, with two well defined seasons: the humid, from October to May, and the dry, from June to September. The total accumulated precipitation between September 2007 and august 2008 was 2498 mm. Using the water balance method, runoff accounted for 10% of this amount (247 mm), evapotranspiration 69% (1734 mm) and recharge 21% (517 mm). Water table was monitored in two wells with different depths in the unconfined aquifer, between September 2008 and April 2010. The total precipitation during this period was 2742 mm. Using the water table fluctuation method, recharge in the shallower well was 20% of this total (544 mm), and 16% in the deeper well (456 mm). Only rainfalls in excess of 100 mm/month caused an elevation in the water table. The local meteoric line was established (D = 8,5 18O + 17 ( VSMOW)). The stable hydrogen and oxygen isotopes indicated that the main recharge source is rainfall, and a secondary source is leakage from water and sewage mains. Radioactive Pb isotopes were not useful for recharge source definition. Water samples collected at different depths in gravel-packed wells show both distinctive radioactive Sr isotope and hydrochemical signatures. Thus, groundwater can classified as shallow, intermediary and deep. Most samples collected at gravel-packed wells had less than 8% of water coming from the shallow zone, but a few wells had up to 49% of shallow water, which indicates high vulnerability to contaminants. Therefore, Sr isotopes may be used as a tool in unconfined aquifer vulnerability assessments.

Pour la climatisation de bâtiments ou d’installations industrielles, les nappes d’eaux superficielles représentent une source de frigories très convoitée. Leurs exploitations intensives depuis plusieurs dizaines d’années conjuguées au redéploiement de la filière géothermique ces dernières années, soulèvent des préoccupations quant à la préservation des ressources en eau. Dans ce contexte, la présente étude vise à évaluer l’impact de variations locales de température sur la qualité physico-chimique et microbiologique des eaux souterraines sur la base (i) de suivis in-situ au niveau de 3 installations réelles exploitant les nappes d’eaux superficielles et, (ii) d’expérimentations sur un pilote (BIOTHERMEX) permettant de reproduire, en conditions parfaitement maitrisées, l’effet de la propagation d’un panache thermique dans un modèle réduit d’aquifère. Dans la gamme de température relevée sur site, les principaux résultats obtenus montrent que les impacts thermiques sont circonscrits au voisinage immédiat de l’installation, pouvant altérer jusqu’à plus d’une dizaine de degrés la sténothermie des nappes. Le suivi des paramètres physico-chimiques n’ont pas fait apparaitre de perturbations significatives sur la période de surveillance, constat étayé par des modélisations hydrogéochimiques. En revanche, une influence significative a été relevée au niveau des principaux descripteurs microbiologiques (activité, diversité de la microflore totale). Enfin, les expériences menées à l’échelle du laboratoire ont permis d’appréhender finement le comportement réactionnel du système et de définir une température de réinjection critique, au-delà de laquelle des désordres potentiels sont attendus. / The use of shallow groundwater as heat source for heat pump is very coveted for air-conditioning of building or industrial facilities. Their intensive use during many years combined with the redeployment of the geothermal industry these last years, raise concerns about the safeguarding of the water resources. In such a context, the present study aims to evaluate the impact of local variations of temperature on the physicochemical and microbiological quality of groundwater systems on the basis of (I) field investigation and, (II) experiments on a pilot (named BIOTHERMEX) making it possible to reproduce, in perfectly supervised conditions, the effect of the propagation of a thermal plume in a reduced aquifer model. Within the temperature recorded on site, principal outcomes showed that thermal impacts are confined in the immediate vicinity of the installation, and were able to deteriorate, up to about ten degrees, the stenothermy of the groundwater systems. The evolution of the physicochemical parameters did not reveal any significant disturbances over the monitoring period, this being also predicted by hydrogeochemical modeling. On the other hand, a significant influence was raised about some microbiological indicators-descriptors (namely activity, diversity of the total microflora). Lastly, the experiments undertaken on the laboratory scale made it possible to finely apprehend the reactional behavior of the system and to define a critical temperature of re-injection beyond which, potential disorders are expected.

O estudo desenvolveu-se em área de plantação de arroz na região de Águas Claras, Município de Viamão, caracterizada por depósitos arenosos quaternários inconsolidados inseridos no Sistema Laguna-Barreira da Planície Costeira do Rio Grande do Sul. O trabalho teve por objetivo avaliar o impacto do uso intensivo de fertilizantes NPK nos solos e na água do aqüífero livre, verificando a transferência de elementos primários (macro nutrientes), micronutrientes, metais, metalóides e outros elementos-traço (inclusive Elementos Terras Raras) no perfil. Foram coletadas amostras de fertilizante aplicado na área, solos e água em duas áreas fertilizadas e uma não fertilizada (background), realizando-se análises de parâmetros físico-químicos de águas in-loco, análises de difratometria de Raios-X e CTC, e análises multi-elementares com ICP-MS. A coleta de amostras de água foi realizada através de dois poços de monitoramento em três tempos distintos, 6 meses pós-fertilização, duas semanas pré-fertilização e três semanas pós-fertilização. Os solos coletados são classificados como arenosos, contudo, observou-se presença significativa de argila em um perfil. A difração de raios-X identificou presença dos argilominerais ilita e caolinita nas amostras com conteúdo de argila mais elevado. Análises de capacidade de troca de cátions revelaram resultados entre 4,86 e 17,9 cmol/dm3. A condutividade hidráulica do aqüífero freático, registrada através do Teste de Slug resultou em 1,168x10-4 cm/s para o solo do poço com presença maior de argila. No levantamento dos parâmetros de campo observou-se, em quase a totalidade das amostras, as águas possuem pH abaixo de 6 e o conteúdo de sólidos totais dissolvidos situam-se acima do permitido pela Resolução CONAMA 396/08. Os dados químicos de elementos maiores mostram que as águas classificam-se como em praticamente todas as amostras como cloretada-sódico-cálcicas, de acordo com o Diagrama Piper. A análise dos resultados demonstra que o fósforo e magnésio são em sua maior parte adsorvidos no solo, causando efeito cumulativo. Outros elementos químicos que sofreram maior enriquecimento nos solos devido à aplicação de fertilizante foram Al, As, Cd, Cs, Eu, Fe, Li, Mn, Rb, U e V. Nas análises de água detectou-se excesso de manganês, ultrapassando o limite máximo permitido pela Resolução CONAMA 396/08 0,1mg/L, tendo Ce, La e Nd entre os Elementos Terras que tiveram maior enriquecimento. Os resultados demonstram que a aplicação de fertilizantes em aqüíferos com elevada vulnerabilidade pode contaminar as águas subterrâneas, comprometendo sua potabilidade. / This study has been developed in area of rice plantation in the region of Aguas Claras, Municipal District of Viamão, which is comprises quaternary deposits of sandy soils related to the Lagoon-Barrier System of the Rio Grande do Sul Coastal Plain. The main objective was to evaluate the impact of intensive use of fertilizers NPK in the soils and in the free-aquifer, verifying the transfer of primary elements (macronutrients), micronutrients, metals, metalloids and other trace elements (including Elements Rare Earth) in the soil. Samples of fertilizer applied in the plantation, soils, and water in two fertilized areas and in one non-fertilized area (background) were collected. Main physico-chemical parameters of water were measured in the field, while analyses of X-Ray Diffraction, CTC, and multielementary analyses by ICP-MS were processed. The water samples were collected in two monitoring wells in three different periods, 6 months before fertilization, two weeks before fertilization and three weeks after fertilization. The collected soils are classified as sandy, however, significant presence of clay was observed in one profile. The X-Ray Diffraction identified illite and caolinite as the clay minerals phase in samples with higher clay content. Analyses of Cation Exchange Capacity revealed values between 4,86 and 17,9 cmol/dm3. The hydraulic conductivity of the free aquifer through the Slug Test resulted in 1,168x10-4 cm/s for the clayish soil. In the samples majority, the water pH is below 6, and the total dissolved solids is above the limits of the CONAMA Resolution 396/08. The chemical data of major elements show that chlorinated-sodic-calcic water type prevails in the area, according to the Piper Diagram. The chemical results demonstrate that phosphorus and magnesium are mainly adsorved in the soil, causing cumulative effect. Other chemical elements showing higher enrichment in the soil due to fertilizer application were Al, As, Cd, Cs, Eu, Fe, Li, Mn, Rb, U and V. The water analyses detected a manganese excess, according CONAMA Resolution 396/08, while Ce, La and Nd among the REE had larger enrichment. The results clearly demonstrate that intensive fertilizer application in aquifer with high vulnerability can contaminate groundwater.