L’étude a pour objectif de déterminer la qualité des eaux de surface sous différentes conditions climatiques et pratiques de gestion des eaux de surface. Trois sites ont étés choisis pour: (1) la rivière Jalle de Blanquefort, (2) le lac de Bordeaux, France et (3) la rivière Pasig aux Philippines. Les sites français présentent des collecteurs d'eau qui se déversent directement dans les eaux de surface. La rivière Pasig sert de collecteur d'eaux usées en l’absence de stations de traitement des eaux usées et collectées. Au cours des campagnes de mesure, il a été possible de suivre l’impact de la variabilité climatique (pluviométrie) et d’événements aléatoires sur la qualité chimiques (éléments traces métalliques et polluants organiques) des eaux ; en combinant échantillonnage classique et par capteurs passifs. Les propriétés physico-chimiques de l'eau ainsi que les caractéristiques des particules et l'utilisation d'analyses statistiques permettent de préciser le comportement des molécules détectées et de décrire l’evolution hydrochimique des eaux de surface urbaines et estuariennes vis-à-vis d’aléas climatiques contrastés. / The study aimed to assess the water quality of the surface water in differingclimate conditions and management practices. Three interesting sites were chosen, (1)Jalle River and (2) Bordeaux Lac both in France and the (3) Pasig River in thePhilippines. The French sites have rainfall and run-off collectors that directly dischargewater to the water bodies. Pasig River, on the other hand, becomes a waste collector aswaste management and treatment plant are lacking. Trace metals and organics(pesticides, herbicides, pharmaceuticals and drugs) were measured. Conventional andpassive sampling approches were employed. The mass fluxes were obtained in order tocalculate the pollution transport. Physico-chemical properties and the particlecharacteristics, integrating statistical analyses, facilitated in explaining the behavior of themeasured molecules and describing the hydrological system in relation to climatevariability.

The transport of elements by streams from headwater regions to the sea is influenced by landscape characteristics. This thesis focuses on the influence of landscape characteristics (e.g. proportion of wetland/forest coverage) on temporal and spatial variations of Fe, Mn, S and trace elements (As, Co, Pb) in streams located in northern Sweden, a boreal region characterized by coniferous forests and peat wetlands. Water samples from a network of 15 streams revealed a different hydrogeochemistry in forested catchments compared to wetland catchments. The temporal variation was dominated by spring flood, when concentrations of Fe, Mn and trace elements increased in forested headwaters. However, in streams of wetland catchments concentrations decreased, but Pb concentrations were higher in comparison to other streams. Both Fe and Pb showed positive correlations with wetland area, while Co correlated with forest coverage. The anthropogenic contribution of As and Pb appear to be larger than the supply from natural sources. During spring flood SO42- decreased in most streams, although concentrations increased in streams of wetland catchments. Concentrations of SO42- were higher in streams of forested catchments than in wetland dominated streams, the former being net exporters of S and the latter net accumulators. Isotope values of stream water SO42- (δ34SSO4) were close to that of precipitation during spring flood, indicating that the major source of S is from deposition. The results show that, although emissions of anthropogenic S have been reduced, there is still a strong influence of past and current S deposition on runoff in this region. In conclusion, wetlands are key areas for the hydrogeochemistry in this boreal landscape. The findings emphasize the importance of understanding stream water chemistry and element cycling from a landscape perspective. This may be important for predicting how boreal regions respond to environmental disturbances such as climate change.

Ce travail s’inscrit dans un projet de recherche interdisciplinaire (Zone Atelier Bassin du Rhône – Agence de l’Eau Rhône Méditerranée Corse) portant sur la rivière Cèze, affluent du Rhône.Le terrain d’expérimentation se situe dans les formations karstiques du bassin de la Cèze (Gard, France). Cette zone touristique est exposée à une croissance démographique et de l’activité agricole, engendrant une augmentation de la demande en eau. La thèse se concentre sur la restitution des eaux karstiques à la rivière en période estivale pour en comprendre le fonctionnement de l’hydrosystème en période de basses eaux, quand la ressource est vulnérable.Ce travail a permis d’élaborer une méthodologie, pour analyser et quantifier les échanges entre la rivière et l’aquifère karstique, fondée sur : la géologie, l’hydrologie, la géochimie, la biologie, la radioactivité en radon, l’analyse d’images infrarouges thermiques et la modélisation. Les résultats obtenus avec ces approches sont confrontés pour interpréter les interactions karst/rivière d’un point de vue qualitatif et/ou quantitatif (localisation, périodicité, débits). La confrontation de ces résultats met en avant l’intérêt d’une méthodologie interdisciplinaire pour interpréter et quantifier les échanges karst/rivière. L’application de la méthode montre qu’en juin 2015, la Cèze est alimentée à 50 % par des eaux karstiques.L’analyse multi-métrique du système karstique a permis d’acquérir de nouvelles connaissances sur son fonctionnement nécessaires pour paramétrer le modèle par réseaux de neurones qui constitue la dernière étape de ce travail. / This work is part of an interdisciplinary research project (Rhone Basin Workshop Zone – the Rhone-Mediterranean and Corsica Water Agency) on the river Cèze, a tributary of the Rhône.The experimental field is located in the karstic formations of the Cèze basin (Gard, France). This tourist area is exposed to population growth and agricultural activity, causing an increase in water demand. The thesis focuses on the karstic water restitution to the river during summer, in order to understand the functioning of the hydrosystem in periods of low water levels, when the resource is vulnerable.This work led to the development of a methodology to analyze and quantify the exchanges between karstic aquifers and rivers. This methodology is based on geology, hydrology, geochemistry, biology, radon radioactivity, infrared thermal imaging analysis and modeling. The results obtained with these approaches are compared in order to understand the karst/river interactions from a qualitative and/or quantitative point of view (localization, frequency, flow rates). The comparison of these results highlights the advantages of an interdisciplinary methodology for understanding and quantifying the karst/river exchanges. The application of this method shows that in June 2015, 50 % of the river Cèze was fed by karstic waters.The multi-metric analysis of the karstic system has led to new knowledge about its functioning. This knowledge is necessary to set the model’s parameters using neural networks, which is the last stage of this work.

<div> <p>Despite its location in the rain shadow of the southern Sierra Nevada, the Panamint Range within Death Valley National Park, CA hosts a complex aquifer system that supports numerous springs. These springs, in turn, support unique groundwater-dependent ecological communities. Spring emergences range in elevation from 2434 m above sea level (within the mountain block) to 77 m below sea level (in the adjacent basins). Waters were collected from representative Panamint Range springs and analyzed for environmental isotopes and geochemical tracers to address the following questions: 1) What is the primary source of recharge for the springs? How much recharge occurs on the Panamint Range? 2) What groundwater flowpaths and geologic units support springflow generation? and 3) What are the residence times of the springs? The stable isotopic composition (δ¹⁸O and δ²H) of spring water and precipitation indicate that localized high-elevation snowmelt is the dominant source of recharge to these perennial springs, though recharge from rainfall is not wholly insignificant. Geochemical evolution was evaluated using principle component analysis to compare the concentrations of all major spring cations and anions in a multidimensional space and group them according to dominant geochemical signatures. These resulting geochemical groups are controlled primarily by topography. The Noonday Dolomite and other carbonate units in the range are identified as the water-bearing units in the mountain block based on the ⁸⁷Sr/⁸⁶Sr of spring waters and rock samples. These units also offer higher hydraulic conductivities than other formations and are chemically similar. Radiocarbon- and ³H derived residence times of these spring waters range from modern to approximately 1840 years, with the shortest residence times at higher altitudes and Hanaupah Canyon and increasing residence times with decreasing altitude. This residence time-altitude relationship is likewise likely topography-driven though there are significant disparities in mountain block storage between the various canyons of the range resulting in variable residence times between drainages. Lower Warm Springs A and B, however, are the exceptions to this trend as they emerge at lower altitudes (750m above sea level) and are likely driven by the transport of groundwater to the surface along faults which increases both the temperature and groundwater residence times of waters from these springs. Benthic macroinvertebrates and benthic and planktonic microbes were also sampled for each spring studied. BMI and microbial community structure in the Panamint Range is likewise topography-controlled with more tolerant communities at lower elevations (within more chemically evolved waters) and less tolerant species in the unevolved waters at higher elevations.</p></div>

The Pimpama estuarine plain in subtropical southeast Queensland is comprised of Quaternary sediments infilling older bedrock. These multilayered unconsolidated sediments have various depositional origins, and are highly heterogeneous. The plain is low-lying and the surface drainage is controlled by flood mitigation measures including tidal gates and channelised streams. The control of surface drainage potentially affects the shallow water table. This modification of hydrology has implications for future viability of agriculture and also the environmental health of waterways. Increased landscape modification and water management is likely in the coming years. The combination of sediment heterogeneity, low hydraulic gradients, and artificial drainage modification result in the plain being hydrogeologically complex. In order to understand hydrologic processes in this setting, a multi-disciplinary research programme was conducted which included a drilling program, overland electromagnetic induction and other geophysical surveys (downhole gamma log, electromagnetic induction and magnetic susceptibility) to initially establish the geologic framework. These surveys were followed by hydrogeochemical testing which includes for major and minor ions and also stable isotopes, and mineralogical analysis of drillhole material. Underlying basement rock occurs at up to 60 m depth. Unconsolidated gravel and sand deposits occur within incised paleo-valleys and are overlain by predominantly low-permeability fluvial sandy clays and estuarine and lagoonal muds. Fine-grained delta sands occur in the top 15 m of the sub-surface. Within the unconsolidated sediments, hydrodynamic trends clearly discriminated between upper unconfined and lower semi-confined aquifer systems. A comparison of surface water and shallow groundwater levels indicate limited interaction of groundwater and surface water. Hydrogeochemical analysis effectively distinguished between groundwater bodies, and also distinguished saline groundwater from seawater. Trends in major ion chemistry in the semi-confined system (particularly Na/Cl and Ca/Cl ratios) showed ion exchange accompanying saline intrusion. However, due to factors such as mineral dissolution, major ion chemistry does not clearly identify solute flux trends in the shallow aquifer system. Water stable isotope analysis (δ18O and δ2H) indicated the provenance of fresh and saline groundwater and also the relative importance of the principal hydrologic processes, i.e. evaporation and water uptake by plants. Groundwater exhibited a wide range in salinity, from very fresh to hypersaline. The formation of hypersaline groundwater was attributed largely to uptake of water by mangrove forests. Since mangrove forests were more extensive at the time of the Holocene maximum sea level (approximately 6,000 years ago) than at present, some of this groundwater may represent relict salinity from this earlier time. The relationship of relict salinity to low permeability sediments, particularly at intermediate depths, and their depositional history was examined. Vertical salinity gradients and hydrogeochemistry within these sediments varied according to position within the plain, suggesting deposition under various hydrological and sea level regimes. A preliminary investigation using analysis of stable sulfate isotopes (δ34S and δ18OSO4) was made. This study shows substantial potential for the application of this technique for quantification of solute flux and sulfur chemical transformations within settings such as this coastal plain. To establish shallow groundwater flow processes, a MODFLOW-based numerical model was used to inversely estimate aquifer parameters under various recharge scenarios. The model was designed to examine the relative importance of evapotranspiration and discharge to surface waters. However, largely due to the complexity of the drainage network and non-uniform surface water flows, the quantification of surface water- groundwater interaction by consideration of hydrodynamics is problematic. Therefore, the chemistry of groundwater and surface water was compared. While the estimated contribution of rainfall to groundwater level fluctuations was significant (46%), high evapotranspiration rates reduced net recharge and it was concluded that baseflow to drains and creeks during dry periods was insignificant, and groundwater velocities in the shallow aquifer are low. The study illustrates the value of both hydrodynamic and hydrogeochemical analyses in estuarine settings where relict salinity and groundwater-aquifer interactions impact significantly on water quality. Saline groundwater is chemically distinct from theoretical mixtures of seawater and freshwater. The study also demonstrates the value of particular chemical parameters, e.g. Na/Cl and SO4/Cl ratios and stable water isotopes, for identifying hydrologic processes in this setting.

La premier thématique a pour objectifs :1) de tracer l’origine de la salinité des eaux des aquifères karstiques en milieu côtier méditerranéen,2) de quantifier les proportions de mélange entre les eaux salées et les eaux karstiques,3) de discriminer les traceurs géochimiques pour identifier et modéliser les processus de salinisation d’aquifères karstiques côtiers. La seconde thématique a pour objectifs:1) d’établir les [As] d’origine naturelle des eaux de surface et des eaux souterraines, 2) de quantifier le niveau de contamination en arsenic de ces eaux et sa variabilité spatio-temporelle 3) de tracer l’origine naturelle ou anthropique de la pollution en As à l’aide d’outils isotopiques adaptés. les origines de la salinité identifié inclue i) des venues d’eaux profondes salées ii) des venues profondes d’eau salées remontant vers la surface par une faille majeure normale. Le 36Cl/Cl a permis d’identifier l’origine profonde des eaux salées et une recharge d’eau météorique infiltrée lors de la période des essais thermonucléaires. La modélisation PHREEQC permet de différentier le mélange avec une eau profonde salée de celui avec une eau de mer actuelle. Le 87Sr/86Sr montre un comportement conservatif pour tracer l’origine des eaux salées dans les aquifères karstiques. Les traceurs Cs, Rb, Li et B permettent de différentier les trois origines identifiées de la salinité. Les données acquises sur la contamination en As soulignent une augmentation nette et pérenne des [As] à partir des anciens sites de traitement minier réhabilités. Les rapports 87Sr/86Sr et δ18O et δ2H se révèlent dans ce cas un traceur très discriminant de l’origine naturelle ou anthropique de l’arsenic. / The first theme has for objectives: 1) to trace the origin of the salinity of the waters of the karst aquifers in coastal environment mediterraneen,2) to quantify the mixing proportions between salt waters and the waters karstiques,3) to discriminate the geochemical tracers to identify and model the process of salinization of aquifers coastal karst. The second theme has for objectives:1) to establish the [hast] of natural origin of surface waters and groundwater, 2) to quantify the level of contamination by arsenic in these waters and its spatial and temporal variability 3) to trace the natural or anthropogenic origin of pollution in hast to the aid of isotopic tools adapted. the origins of the salinity identified include i) of came from deep waters salted ii) of come deep water salted dating back toward the surface by a major flaw normal. The 36Cl/Cl has allowed us to identify the origin of deep saline waters and a recharge of meteoric water infiltrated during the period of thermonuclear tests. The PHREEQC modeling used to differentiate between the mixture with a deep water of salt that one with a sea water current. The 87SR/ 86Sr shows a conservative behavior for tracing the origin of saline waters in karst aquifers. The plotters Cs, Rb, Li and B allows to differentiate the three origins identified of salinity. The data acquired on the contamination in hast underline a net increase and perennial of [hast] from the ancient sites of mining processing rehabilitated. The reports 87SR/ 86Sr and δ18O and δ2H will reveal in this case a chartplotter very discriminant of natural or anthropogenic origin of arsenic.

PhD (Environmental Sciences) / Department of Ecology and Resource Management / The presence of arsenic in groundwater has drawn worldwide attention from researchers and public health officials due to its effects on human health such as, cancer, skin thickening, neurological disorders, muscular weakness, loss of appetite and nausea. World Health Organisation (WHO) has set the limit of 10 μg/L for arsenic in drinking water in trying to reduce the effects of arsenic. This was further adopted by South African National Standard (SANS). The present study aims at evaluating arsenic concentration in selected groundwater sources around Greater Giyani Municipality in Limpopo Province and further synthesize clay based adsorbents for arsenic removal using Fe3+ and Mn2+ oxides and hexadecylammonium bromide (HDTMA-Br) cationic surfactant as modifying agents. The first section of the work presented the hydrogeochemical characteristics of groundwater in the Greater Giyani Municipality. The results showed that the pH of the samples ranges from neutral to weakly alkaline. The dominance of major anionic and cationic species was found to be in the order: HCO3 ->Cl->SO4 2->NO3 - and Na+>Mg2+>Ca2+>K+>Si4+, respectively. Hydrogeochemical facies identified in the study area include CaHCO3 (90%) and mixed CaNaHCO3 (10%) which shows the dominance of water-rock interaction. About 60% of the tested samples contains arsenic concentration above 10 μg/L as recommended by SANS and WHO. Concentration of arsenic was found to be ranging between 0.1 to 172.53 μg/L with the average of 32.21 μg/L. In the second part of this work, arsenic removal efficiency of locally available smectite rich and kaolin clay was evaluated. Results showed that the percentage As(V) removal by kaolin clay was optimum at pH 2 while the percentage As(III) removal was greater than 60% at pH 2 to 12. For smectite rich clay soils, the percentage of As(III) and As(V) removal was found to be optimum at pH between 6 and 8. The adsorption isotherm data for As(III) and As(V) removal by both clays fitted better to Freundlich isotherm. Adsorption of both species of arsenic onto the clay mineral occurred via electrostatic attraction and ion exchange mechanisms. Both clay soils could be regenerated twice using Na2CO3 as a regenerant. Kaolin clay showed a better performance and was selected for further modification. In the third section of this work, Fe-Mn bimetal oxide modified kaolin clay was successfully synthesized by precipitating Fe3+ and Mn2+ metal oxides to the interlayer surface of kaolin clay. Modification of kaolin clay increased the surface area from 19.2 m2/g to 29.8 m2/g and further v decreased the pore diameter from 9.54 to 8.5 nm. The adsorption data fitted to the pseudo second order of reaction kinetics indicating that adsorption of As(III) and As(V) occurred via chemisorption. The adsorption isotherm data was described by Langmuir isotherm models showing a maximum As(III) and As(V) adsorption capacities of 2.16 and 1.56 mg/g, respectively at a temperature of 289 K. Synthesized adsorbent was successfully reused for 6 adsorptiondesorption cycles using K2SO4 as a regenerant. Column experiments showed that maximum breakthrough volume of ≈2 L could be treated after 6 hours using 5 g adsorbent dosage. Furthermore, the concentration of Fe and Mn were within the WHO permissible limit. In the fourth part of the work kaolin clay was functionalized with hexadecyltrimethylamonium bromide (HDTMA-Br) cationic surfactant and its application in arsenic removal from groundwater was investigated. The results revealed that adsorption of As(III) and As(V) is optimum at pH range 4-8. The maximum As(III) and As(V) adsorption capacities were found 2.33 and 2.88 mg/g, respectively after 60 min contact time. Pseudo first order model of reaction kinetics described the adsorption data for As(V) better while pseudo second order model described As(III) adsorption data. The adsorption isotherm data for As(III) and As(V) fitted well to Langmuir model indicating that adsorption of both species occurred on a mono-layered surface. Adsorption thermodynamics model revealed that adsorption of As(III) and As(V) was spontaneous and exothermic. The As(III)/As(V) adsorption mechanism was ascribed to electrostatic attraction and ion exchange. The regeneration study showed that synthesized adsorbent can be used for up to 5 times. In the firth part of the work inorgano-organo modified kaolin clay was successfully synthesized through intercalation of Fe3+ and Mn2+ metal oxides and HDTMA-Br surfactant onto the interlayers of the clay mineral. The batch experiments showed that As(III) removal was optimum at pH range of 4-6, while the As(V) removal was optimum at pH range 4-8. The adsorption data for both species of arsenic showed a better fit to pseudo second order of reaction kinetics which suggest that the dominant mechanism of adsorption was chemisorption. The isotherm studies showed better fit to Langmuir isotherm model as compared to Freundlich model. The maximum adsorption capacity As(III) and As(V) at room temperature as determined by Langmuir model were found to be 7.99 mg/g and 7.32 mg/g, respectively. The thermodynamic studies for sorption of As(III) and As(V) showed negative value of ΔGᴼ and ΔHᴼ indicating that adsorption process occurred spontaneously and is exothermic in nature. The regeneration study showed that the vi inorgano-organo modified kaolin clay can be reused for up 7 adsorption-regeneration cycles using 0.01 M HCl as a regenerant. Thomas kinetic model and Yoon-Nelson model showed that the rate of adsorption increases with increasing flow rate and initial concentration and decreases with increasing of the bed mass. In conclusions, adsorbents synthesized from this work showed a better performance as compared to other adsorbents available in the literature. Among the synthesized adsorbents, inorgano-organo modified clay showed highest adsorption capacity as compared to surfactant functionalized and Fe-Mn bimetal oxides modified kaolin clay. However, all adsorbents were recommended for use in arsenic remediation from groundwater. The following recommendations were made following the findings from this study: 1) routine monitoring of arsenic in groundwater of Greater Giyani Municipality, 2) evaluating the possible link between arsenic exposure and arsenic related diseases within Giyani in order to find the extent of the problem in order to establish the population at risk, 3) The toxicity assessment for HDTMA-Br modified kaolin clay should be carried out, 4) Materials developed in the present study should be modeled and tested at the point of use for arsenic removal, and lastly, 5) this study further encourage the development of other arsenic removal materials that can be used at household level. / NRF

Groundwater chemistry on the Niagara Peninsula has been identified as highly mineralized in comparison to groundwaters collected from the same bedrock formations elsewhere in southern Ontario. Three geochemical zones were discerned using hierarchical cluster analysis and other geochemical and isotopic methods. The Escarpment Zone, located along the Niagara and Onondaga Escarpments, is characterized by unconfined aquifer conditions, parameters reflective of surficial contaminants, including road salt, and elevated HCO3, DOC, NO3-, coliform bacteria and tritium. In contrast, in the Salina Zone thick, low-permeability sediments and gypsiferous bedrock results in highly mineralized groundwaters with Ca-SO4 geochemical facies and elevated S2-, Ca2+, Mg2+, K+, Na+, SO42-, Cl-, Br-, Sr2+, NH4+ and CH4. The Guelph Zone contains the lowest electrical conductivity of the three zones and elevated F-. Outliers exist with groundwater geochemistry that differs from the local geochemical zone and the host aquifer. These sites have elevated SO42- (>1000 to 5200 mg/L) with depleted δ34SSO4 (-2.2 to 14.3‰ VCDT) signatures that differs starkly from Devonian and Silurian evaporites (~20 to 32 ‰) in the host formations. This exogenic SO4 was identified in a cross-formational northeast – southwest linear trend crossing three major groundwater flow systems. The lack of down-stream impact in these systems and tritium groundwater ages that are typically only decades old indicate a young, non-geological origin and implicate anthropogenic activities. Additionally, nine samples were identified with elevated methane concentrations and δ13CCH4 signatures within the thermogenic range. As thermogenic methane is not produced within shallow aquifers and would be short-lived in the presence of the ubiquitous sulfate, these samples imply recent upward migration of methane from depth through vertical conduits. Taken together, the evidence supports large-scale upward movement of fluids in the centre of the Niagara geochemical anomaly and more sporadic upward transport of gases over a wider area of the peninsula. The most likely vector is through corroded and leaking casings or boreholes of abandoned (century) gas wells that are common across the peninsula. / Thesis / Master of Science (MSc)