Thesis advisor: Rudolph Hon / Thesis advisor: Yvette Kuiper / Chloride-based deicers (NaCl, CaCl₂, MgCl₂), also referred to as road salt, are the most common substances used in maintaining safe roadway surfaces during the winter months. Upon application, road salt reacts with the accumulated snow or ice to form brine equilibrium solutions along the liquidus line in the salt-water system. Dissolved salts dissociate, leading to increased concentrations of the respective ions in nearby soils, surface water, and groundwater. Of the ions present in road salt, chloride has the advantage of tracking all chloride deicers at the same time and since chloride ions are conservative tracers in soils it stays unaffected by ionic exchange interferences. This study explores the mechanisms of chloride return flows by investigating chloride dissolved loads, chloride concentrations in stream waters, seasonal patterns, and changes over the course of four years in two separate watersheds in Massachusetts with differing degrees of urbanization. The chloride tracking technique used in this study is based on calibrated chloride concentrations obtained from specific conductance signals recorded every 15 minutes by automatic recording systems at two locations, one in rural central Massachusetts and the other in urban eastern Massachusetts. These systems are maintained by the USGS, which also provide the simultaneously recorded stream flow datasets. The dissolved chloride load carried by each river is calculated for each single 15-minute interval by multiplying water volume with the corresponding chloride concentration, resulting in a total of over 34,000 data points per annum per site. Hydrograph separation techniques were used to separate dissolved load transported by each river into two separate flow components, event flow resulting from precipitation events, and baseflow resulting from groundwater discharge. Well defined hydrograph baseflow supported periods yield consistent chloride concentrations independent of the season at either urban or rural study sites. Comparison of direct runoff dissolved chloride loads with the total annual dissolved loads suggests that only a small fraction of the deicers actually removed during the overland runoff events and that a minimum of 60% of the total load discharged each year in both urban and rural systems is transported by groundwater. From groundwater recharge by brines rural watersheds are currently retaining as much as 95% of the total chloride applied to roadways each year while urban and suburban watersheds may only retain 75% of the total chloride applied to roadways each year. The increased retention of chloride in rural areas is likely due to the decreased amount of chloride transported during winter seasons as event flow compared to urban watersheds. / Thesis (MS) — Boston College, 2009. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Geology and Geophysics.

Previous hydrometric studies demonstrated the prevalence of overland flow as a hydrological pathway in the tropical rain forest catchment of South Creek, northeast Queensland. The purpose of this study was to consider this information in a mixing analysis with the aim of identifying sources of, and of estimating their contribution to, storm flow during two events in February 1993. K and acid-neutralizing capacity (ANC) were used as tracers because they provided the best separation of the potential sources, saturation overland flow, soil water from depths of 0.3, 0.6, and 1.2 m, and hillslope groundwater in a two-dimensional mixing plot. It was necessary to distinguish between saturation overland flow, generated at the soil surface and following unchanneled pathways, and overland flow in incised pathways. This latter type of overland flow was a mixture of saturation overland flow (event water) with high concentrations of K and a low ANC, soil water (preevent water) with low concentrations of K and a low ANC, and groundwater (preevent water) with low concentrations of K and a high ANC. The same sources explained the streamwater chemistry during the two events with strongly differing rainfall and antecedent moisture conditions. The contribution of saturation overland flow dominated the storm flow during the first, high-intensity, 178-mm event, while the contribution of soil water reached 50% during peak flow of the second, low-intensity, 44-mm event 5 days later. This latter result is remarkably similar to soil water contributions to storm flow in mountainous forested catchments of the southeastern United States. In terms of event and preevent water the storm flow hydrograph of the high-intensity event is dominated by event water and that of the low-intensity event by preevent water. This study highlights the problems of applying mixing analyses to overland flow-dominated catchments and soil environments with a poorly developed vertical chemical zonation and emphasizes the need for independent hydrometric information for a complete characterization of watershed hydrology and chemistry.

Magister Scientiae - MSc (Environ & Water Science) / Studies have shown that the primary origin of salinity in river flows of the Sandspruit in the Berg Catchment located in the Western Cape Province of South Africa was mainly a result of atmospheric deposition of salts. The salts are transported to rivers through surface runoff and subsurface flow (i.e. through flow and groundwater flow). The purpose of this study was to determine the contributions of subsurface and surface flows to the total flows in the Sandspruit, Berg Catchment. Three rain events were studied. Water samples for two rain events were analysed for environmental tracers ?18O, Silica or Silicon dioxide (SiO2), Calcium (Ca2+) and Magnesium (Mg2+). Tracers used for two component hydrograph separation were ?18O and SiO2. The tracers, Ca2+ and Mg2+, revealed inconsistent contributions of both subsurface flow and surface flow. Two component hydrograph separations indicated is that groundwater is the dominant contributor to flow, while surface runoff mainly contributes during the onset of the storm event. Groundwater response to precipitation input indicated that boreholes near the river have a quicker response than boreholes further away from the river. Boreholes nearer to the river also indicate higher water levels in response to precipitation, in comparison to boreholes further from the river.

Magister Scientiae - MSc (Environ & Water Science) / Studies have shown that the primary origin of salinity in river flows of the Sandspruit in the Berg Catchment located in the Western Cape Province of South Africa was mainly a result of atmospheric deposition of salts. The salts are transported to rivers through surface runoff and subsurface flow (i.e. through flow and groundwater flow). The purpose of this study was to determine the contributions of subsurface and surface flows to the total flows in the Sandspruit, Berg Catchment. Three rain events were studied. Water samples for two rain events were analysed for environmental tracers ?18O, Silica or Silicon dioxide (SiO2), Calcium (Ca2+) and Magnesium (Mg2+). Tracers used for two component hydrograph separation were ?18O and SiO2. The tracers, Ca2+ and Mg2+, revealed inconsistent contributions of both subsurface flow and surface flow. Two component hydrograph separations indicated is that groundwater is the dominant contributor to flow, while surface runoff mainly contributes during the onset of the storm event. Groundwater response to precipitation input indicated that boreholes near the river have a quicker response than boreholes further away from the river. Boreholes nearer to the river also indicate higher water levels in response to precipitation, in comparison to boreholes further from the river.

付記する学位プログラム名: グローバル生存学大学院連携プログラム / 京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第20341号 / 工博第4278号 / 新制||工||1662(附属図書館) / 京都大学大学院工学研究科社会基盤工学専攻 / (主査)教授 寶 馨, 教授 立川 康人, 准教授 佐山 敬洋 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

The Mississippi Alluvial Plain, a robust agricultural region in the South-Central United States, provides commodities across the United States and around the world. Water for irrigation, which is necessary due to irregular rainfall patterns during the growing season, is withdrawn largely from the Mississippi River Valley Alluvial aquifer, one of the most intensely used aquifers in the United States. The groundwater-dependent region has observed recent declines in groundwater and streamflow levels, raising concerns about the availability and use of fresh-water resources. Declining water levels have prompted investigation into the current understanding of groundwater and surface-water interaction. Previous research does not adequately quantify the unobservable exchange of water between surface-water bodies and the underlying aquifer. This research was designed to advance the current understanding of the interaction between groundwater and surface water through the quantification of spatial and temporal trends in streamflow and groundwater level changes and the use of high-resolution spatial estimates of streambed hydraulic conductivity. Changes in streamflow and groundwater levels were quantified with the use of hydrograph-separation techniques and trend analyses. High-resolution estimates of streambed hydraulic conductivity were found through the correlation of waterborne continuous resistivity profiling data to hydraulic conductivity and streambed hydraulic conductivity estimates were incorporated into the existing Mississippi Embayment Regional Aquifer Study (MERAS) groundwaterlow model. Site-specific empirical relationships between resistivity and hydraulic conductivity were developed with near-stream borehole geophysical logs to improve model estimates of streambed hydraulic conductivity. Results of the quantification of changes in streamflow and groundwater levels suggested agricultural groundwater withdrawals for irrigation to be the primary source of groundwater-level declines. Results from the incorporation of high-resolution estimates of streambed hydraulic conductivity showed that the existing groundwaterlow model is sensitive to changes in streambed hydraulic conductivity, which may impact model accuracy. The incorporation of streambed hydraulic conductivity estimates derived from site-specific empirical relationships impacted MERAS model water-budget estimates. Information gained from this research will be used to improve the existing groundwaterlow model, which acts as a decision-support tool for water-resource managers at state and local levels to make informed water-use decisions for the conservation of fresh-water resources for sustainable agricultural irrigation practices.

Near-level Prairie landscapes have received limited attention in hydrological research. For this thesis, hydrometric measurements and four tracing experiments were completed at three “riparian-to-stream” sites in the Catfish Creek Watershed (southeastern Manitoba) to enhance Prairie hydrology understanding. First, hydrologic state variables were examined to infer vertical and lateral water movement. Second, tracer data were analyzed to evaluate the relative importance of surface versus subsurface water movement. Results show that hydrologic state variables can be useful for inferring riparian-to-stream water movement. Tracer data also revealed that subsurface water movement can contribute significantly to streamflow during snowmelt- and rainfall-triggered events in the study watershed. This thesis demonstrated that subsurface flow is a significant runoff generation mechanism in Prairie landscapes, thus challenging surface water-focused conceptualizations and management strategies that are traditionally used. The findings summarized in this thesis will be critical to improve the performance of hydrological models when applied to the Prairies. / February 2017

Orientador: Didier Gastmans / Resumo: A necessidade do estudo os diferentes processos do ciclo hidrológico de forma integrada tem se tornado cada vez mais urgente, uma vez que o uso do termo “crise hídrica” se torna cada vez mais frequente. Nesse sentido, a determinação de taxas de recarga e quantificação dos fluxos subterrâneos, aliados ao uso de isótopos estáveis (2H e 18O), que são excelentes traçadores da movimentação da água no ciclo hidrológico, impulsionaram esse estudo, buscando gerar informações científicas fundamentais para uma melhor gestão dos recursos hídricos. Situada numa porção de afloramento do Sistema Aquífero Guarani (SAG), a área de estudo está inserida em uma pequena bacia hidrográfica na porção oeste do estado de São Paulo, onde as águas subterrâneas e superficiais são responsáveis pelo abastecimento de inúmeras cidades da região. O estudo teve como principal objetivo compreender a dinâmica entre os diversos compartimentos do ciclo hidrológico, buscando mudanças nos padrões de precipitação e de recarga subterrânea, por métodos de fácil aplicação, como balanço hídrico e flutuações dos níveis d’água (WTF), bem como a aplicação de traçadores isotópicos (δ2H e δ18O) em diferentes sazonalidades. Ao considerar a sazonalidade dos dados isotópicos na chuva, águas superficiais e subterrâneas, pode-se observar que os valores de δ18O são mais empobrecidos durante a estação chuvosa e mais enriquecidos durante a estação seca. A diferença entre os sinais isotópicos permitiu compreender a movimentação da á... (Resumo completo, clicar acesso eletrônico abaixo) / Abstract: The need to study the different processes of the hydrological cycle in an integrated way has become increasingly urgent since the use of the term "water crisis" becomes more and more frequent. In this sense, the determination of rates of recharge and quantification of the underground flows, together with the use of stable isotopes (2H and 18O), which are excellent tracers of water movement in the hydrological cycle, stimulated this study, seeking to generate scientific information fundamental to better management of water resources. Located in a portion of the outcrop of the Guarani Aquifer System (SAG), the study area is in a small hydrographic basin in the western portion of the state of São Paulo, where groundwater and surface waters are responsible for the supply of numerous cities located there. The main objective of this study is to understand the dynamics between the various compartments of the hydrological cycle, searching for changes in precipitation and underground recharge patterns, using easy-to-apply methods such as water balance and water level fluctuations (WTF), as well as the application of isotopic tracers (δ2H and δ18O) in different seasonal conditions. When considering the seasonality of the isotopic data in rainfall, surface water, and groundwater, it can be observed that δ18O values are more depleted during the rainy season and more enriched during the dry season. The difference between the isotopic signals allowed to understand the movement of the water... (Complete abstract click electronic access below) / Doutor

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In agricultural catchments, hydrological processes play an important role in the export of nutrients. Water that enters a catchment during a rain event (event water) can have different flow paths and residence times. These affect the transport and biogeochemical transformation of nutrients until the water discharges at the outlet where catchments are usually monitored.This work focused on the contributions of event water and pre-event water (water that was already stored in the catchment before a rainfall event) to the stream. The work is necessary for further studies to develop an understanding of the relation of nutrients export and water flow paths. The method was based on isotopic hydrograph separation and performed on existing data. The stable isotope signature of oxygen in water (δ18O) was used as a tracer. A new study is planned using δ18O to distinguish different flow paths and residence times of water, and therefore a sequential rainfall collector was tested and improved for this purpose.The results of the hydrograph separation show that up to 54% of an increased discharge from a rainwater event is event water, but also that data in a higher temporal resolution is needed to quantify contributions of event water to the runoff for all the events. Additional and more advanced experiments of the rainfall collector would be an advantage, but it can also be used in the field as it is today. Based on the analysis and the revised sequential rainfall collector, a sampling strategy for future work is described. / I ett jordbruksavrinningsområde spelar hydrologiska processer en viktig roll vid export av näringsämnen. Vatten som adderas till ett avrinningsområde från ett regnevent (eventvatten) kan ha olika flödesvägar och olika uppehållstider. Dessa påverkar transporten och omvandlingen av biogeokemiska näringsämnen olika tills det att vattnet lämnar avrinningsområdet via ett utlopp.Arbetet har fokuserat på vilket bidrag eventvatten och vatten som redan lagrats i avrinningsområdet före regnhändelsen (pre-eventvatten) har till avrinningen till en flod. Arbetet är viktigt för att utveckla en förståelse för vattenflödesvägar som är nödvändiga för ytterligare undersökning av export av näringsämnen. Metoden baserades på en isotopisk hydrograf-separation och utfördes på existerande data. Spåraren som användes var den stabila isotopen av syre i vatten (δ18O). Eftersom en ny studie planeras med användning av δ18O för att skilja olika flödesvägar och uppehållstider för vatten, har en sekventiell regnuppfångare också testats och förbättras.Resultaten av den hydrografa separationen visar att upp till 54% av en ökad avrinning i floden som resultat av ett regnevent är eventvatten, men även att det finns behov av data med högre tidsmässig upplösning behövs för att kunna kvantifiera bidrag från eventvatten till avrinningen för alla event. Fler och mer avancerade tester av regnfångaren skulle vara en fördel, men den kan även i dagsläget användas i fält. Baserat på resultat från experiment av regnuppfångaren föreslås kort en provtagningsstrategi för framtida arbeten.