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.

Thesis advisor: Rudolph Hon / Road de-icing salts (predominantly NaCl, CaCl2, and MgCl2) are applied each winter in the northern US, northern Europe, and Canada to maintain safe driving conditions. It is widely recognized that road salt enters the environment through runoff and infiltration (Williams et al., 2000; Ostendorf, et al., 2001; J. Marsalek, 2003), resulting in salinization of freshwater (Godwin et al., 2003; Kaushal et al., 2005; Kelly et al., 2012). The chloride concentration (a proxy for deicers) has doubled in the last 20 years in the groundwater Norwell, MA, the primary public water supply for the town’s residents, and often exceeds the EPA secondary drinking water standard for chloride. The annual budget TDLCl¬ of Third Herring Brook in Norwell, MA is estimated using specific conductance and discharge datasets to determine the retention of dissolved deicers in the watershed during the study period. The estimated retention rate is between 59% and 78%. / Thesis (MS) — Boston College, 2015. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Earth and Environmental Sciences.

Os métodos geofísicos têm sido utilizados para definir a extensão em área e em profundidade de contaminações causadas por compostos orgânicos ou inorgânicos, uma vez que tais contaminações alteram as propriedades físicas do meio. Este trabalho abrangeu o desenvolvimento de ensaios realizados em laboratório e em campo para verificar a aplicabilidade de minissonda de resistividade, que utiliza quatro eletrodos dispostos segundo o arranjo Wenner em conjunto com uma fonte de corrente e dois multímetros, o que torna possível a execução de uma medida convencional de resistividade em diferentes profundidades à medida que a sonda é cravada no solo. Uma eventual aplicação desta minissonda seria sua utilização na avaliação de salinização secundária de solos. A agroindústria, principalmente no estado de São Paulo, vem utilizando cada vez mais estufas para a produção de frutos e flores, principalmente. Os processos de irrigação, e o microclima criados dentro das estufas, têm causado o incremento da quantidade de sais no solo, uma vez que o solo não é naturalmente lixiviado pela água da chuva. Isto pode comprometer a utilização dessas estufas para fins ligados à agricultura. A salinidade refere-se à presença de sais dissolvidos no solo, na água superficial e subterrânea. A salinização do solo pode estar ligada a processos naturais como a pedogênese do solo ou ao clima local por exemplo, ou pode ter origem secundária, podendo estar relacionada às atividades antrópicas capazes de alterar esta propriedade do meio. O presente trabalho visou testar a aplicabilidade da minissonda de resistividade para a avaliação da salinização secundária de solos. O trabalho foi inicialmente desenvolvido em laboratório, onde foram efetuados experimentos em amostras de solo saturadas com soluções de NaCl em diferentes concentrações. Os resultados obtidos nestes ensaios utilizando um meio arenoso totalmente saturado mostraram que a condutividade elétrica aumenta em função da concentração de NaCl utilizado na solução. Observou-se ainda a relação inversa entre a resistividade aparente calculada e a concentração da solução utilizada. Os ensaios de campo foram executados em duas estufas distintas, que utilizam diferentes técnicas de cultivo, localizadas nos municípios de Holambra e Elias Fausto, e não indicaram correlação entre a condutividade elétrica calculada a partir das resistividades obtidas e a condutividade elétricas medidas em laboratório, nas amostras de solo encaminhadas para análise. Foram analisados também os íons Al, Ba, Ca, Cr, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Zn, e cloretos. Nas duas estufas observa-se correlação entre as condutividades obtidas e alguns dos íons analisados. As diferenças observadas entre as condutividades elétricas calculada e medida, podem estar relacionadas às condições de campo, uma vez que nas duas estufas observou-se porções porosas no solo, a presença de solo argiloso nas estufas, principalmente em Holambra, e à presença dos metais presentes no solo local, conforme mostram os resultados analíticos obtidos. Adicionalmente, durante a realização dos ensaios em laboratório o meio encontrase totalmente saturado, o que não ocorreu nos ensaios realizados em campo, uma vez que na estufa em Holambra o solo estava úmido e na estufa em Elias Fausto apresentava-se bastante seco. As diferenças de umidade também podem ter interferido nos resultados obtidos. Os trabalhos realizados evidenciaram que a minissonda pode ser aplicada para medida de resistividade in situ, porém, seu uso deve se limitar à avaliação de áreas onde o solo é mais arenoso e pouco compactado. / Geophysical methods have been used to define the extension and depth of contaminations caused by organic and inorganic compounds spills. This is because those contaminations change the physical properties of the underground materials. This study presents the tests results performed both in laboratory and field of a small probe that allows the in situ measurement of the resistivity, avoiding the need of installation of monitoring wells and allowing low cost and fast measurements. It consists in a probe with four electrodes according a Wenner array, a current source and two multimeters. It makes possible to take in situ resistivity measurements in different depths while the probe is inserted in the soil. An eventual application for that mini probe would be for evaluation of secondary salinity of the soil. The agro industry, mainly in the São Paulo state, has been using greenhouses to increase the production mainly of fruits and flowers. The irrigation processes used and the microclimate generated in the greenhouse have been causing an increasing salt quantity in the soil. This happens because the natural lixiviation (by the rain) does not occur. That increasing salinization may prejudice the use of such greenhouses for agricultural purposes. Salinization refers to a build up of salts in soil, in the superficial water and groundwater. It may be due to natural process, like e.g. the pedogenesis or the local climate, or it may have a secondary origin, normally related to antropic activities that are capable to modify such property. This study aimed at testing the applicability of the resistivity mini probe to evaluate the secondary salinization of the soil. It was performed firstly in laboratory, using soil samples saturated with NaCl solutions of different concentrations. The results of those experiments showed that the electrical conductivity increases as function of the NaCl concentration and, naturally, the inverse relation with the apparent and calculated resistivity. Field tests were performed in two different greenhouses where distinct techniques are used. They are located in the Holambra and Elias Fausto municipalities. These tests did not indicate correlation between the electrical conductivity calculated from the measures resistivities and the electrical conductivities measured in the soil samples sent to the laboratory. In those samples the ions Al, Ba, Ca, Cr, Co, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Zn, and chloride were also analyzed. For both greenhouses, some ions presented correlation with the electrical conductivities. The observed differences between the electrical conductivity calculated and measured may be related to the field conditions, since that in both greenhouses the soil was porous (avoiding the perfect coupling of the probe), the presence of clay that sticks in the probe between the electrodes, or the presence of metals in the soil, shown by the chemical analysis. In addition, during the laboratory tests, the soil was completely saturated, what was not the case in the field. In Holambra the soil was wet and Elias Fausto it was completely dry. So, the humidity differences may have interfered in the results. Finally, the tests results showed that the mini probe may be applied to measure the resistivity in situ but, its use may be limited to the evaluation of areas where the soil is more sandy and relatively loose.

Uma área de 9 m x 28 m, localizada às margens do açude Cajueiro, no município de Tuparetama - PE, foi instrumentada com o objetivo de estudar os processos de transferência de água e de solutos. O solo local é heterogêneo, sendo constituído por um solo aluvial de características arenosas a franco arenosas. A área, localizada na região semi-árida e utilizada para o cultivo de vazante, está sujeita a altas taxas de evaporação e aos efeitos cíclicos de subida e rebaixamento do nível d\'água do açude. A caracterização física do solo foi feita com base em ensaios de prospecção e granulometria. A caracterização hidráulica foi realizada com base em um ensaio de drenagem interna realizado no centro da área e as concentrações de sais totais presentes no solo foram obtidas pro meio de ensaios de determinação dos sais solúveis em extratos de saturação. Os parâmetros hidráulicos foram obtidos ajustando-se os dados do ensaio de drenagem interna e de monitoração de campo a diversos modelos analíticos, utilizando-se o programa RETC. Os parâmetros hidrodispersivos foram obtidos ajustando-se os dados da curva de eluição experimental aos modelos CDE e CDE-MIM, utilizando-se o programa CXTFIT 2.0. O programa HYDRUS-2D foi utilizado para simular o fluxo de água e o transporte de solutos num domínio de fluxo bi-dimensional com 28 m de comprimento e 2,0 m de profundidade, incluindo a zona saturada e não saturada. O programa simulou bem o comportamento do fluxo medido no campo através da instrumentação. Os valores simulados de umidade se ajustaram melhor aos valores medidos na estação localizada no centro da área instrumentada. Para as camadas superficiais os valores simulados de umidade foram superestimados o que pode estar associado à variabilidade espacial dos parâmetros hidráulicos ou à influência de fluxo preferencial. A simulação do transporte de solutos, feita em termos de sais totais, permitiu concluir que as altas taxas de evaporação, associadas às concentrações de sais totais presentes no solo, tendem a provocar a salinização das camadas superficiais da área estudada. / An area of 9 m x 28 m, located in the banks of the Cajueiro reservoir, in the municipal district of Tuparetama, Pernambuco, has been instrumented with the objective of studying the processes of water flow and solute transport. The local soil is heterogeneous, being constituted by an alluvial soil of sandy characteristics. The area, located in the semi-arid region and used for the agriculture, is subjected to high evaporation rates and cyclical effects of rising and lowering of the water level in the reservoir. The physical characterization of the soil has been undertaken based on sample extraction and texture analysis. The hydraulic characterization has been based on an internal drainage experiment accomplished in the center of the area and the concentrations of present total salts have been obtained from saturation extracts. The hydraulic parameters have been obtained fitting the internal drainage experiment data and the field data to several analytic models, using the program RETC. The hydrodispersive parameters have been obtained fitting the data of breakthrough curves to the models CDE and CDE-MIM, using the program CXTFIT 2.0. The program HYDRUS-2D have been used to simulate the water flow and solute transport in a two-dimensional domain with 28 m of length and 2,0 m of depth, including the saturated and unsaturated zones. The program has simulated well the behavior of the flow measured in the field. The simulated values of water content agreed better with the measured values in the center of the studied area. For the superficial layers the simulated values of water content have been overestimated, which can be associated to both the spacial variability of the hydraulic parameters and the influence of preferential flow. The simulation of the solutes-transport, in terms of total salts, has shown that the high evaporation rates in association to the salts presents in the soil promote the salinization of the superficial layers of the studied area.

Spicers Creek catchment is located approximately 400 km west of Sydney in the Central West region of New South Wales, Australia. Dryland salinity has been recognised as a major environmental issue impacting soil and water resources in the Central West region of NSW for over 70 years. Due to the geological complexity of the catchment and the presence of high salt loads contained within the soils, groundwater and surface waters, the Spicers Creek catchment was identified as a large contributor of salinity to the Macquarie River catchment. Over fifty-two dryland salinity occurrences have been identified in the Spicers Creek catchment and it appears that dryland salinity is controlled by the presence of geological structures and permeability contrasts in the shallow aquifer system. Combinations of climatic, geological and agricultural factors are escalating salinity problems in the catchment. The main aim of this thesis was to identify the factors affecting salinisation processes in the Spicers Creek catchment. These include the role of geological structures, the source(s) of salts to the groundwater system and the geochemical processes influencing seepage zone development. To achieve these aims a multidisciplinary approach was untaken to understand the soils, geology, hydrogeology and hydrogeochemistry of the catchment. Investigative techniques employed in this project include the use of geophysics, soil chemistry, soil spectroscopy, hydrogeochemistry and environmental isotopes. Evaluation of high-resolution airborne magnetics data showed a major north-east to south-west trending shear zone. This structure dissects the catchment and several other minor faults were observed to be splays off this major structure. These structures were found to be conducive to groundwater flow and are influencing the groundwater chemistry in the fractured aquifer system. Two distinctive groundwater chemical types were identified in the catchment; the saline Na(Mg)-Cl-rich groundwaters associated with the fractured Oakdale Formation and the Na-HCO3-rich groundwaters associated with the intermediate groundwater system. The groundwater chemistry of other deep groundwaters in the catchment appears to be due to mixing between these end-member groundwaters within the fractured bedrock system. The spatial distribution of electrical conductivity, Cl-, Sr2+ and 87Sr/86Sr isotopic ratios showed the correlation between saline groundwaters and the location of faults. Elevated salinities were associated with the location of two crosscutting fault zones. The spatial distribution of HCO3-, K+, Li+ and ?????3CDIC highlighted the extent of Na-HCO3-rich groundwaters in the catchment and showed that these groundwaters are mixing further east than previously envisaged. These findings show that Na(Mg)-Cl-rich groundwaters are geochemically distinctive and have evolved due to extensive water-rock interaction processes within the fracture zones of the Oakdale Formation. These saline groundwaters contain elevated concentrations of trace elements such as As, V and Se, which pose a potential risk for water resources in the area. 87Sr/86Sr isotopic ratios indicated that the source of salinity to the Na(Mg)-Cl-rich groundwaters was not purely from marine or aerosol input. Salt is most likely contributed from various allochthonous and autochthonous sources. This research found that the main mechanism controlling the formation of dryland salinity seepage zones in the Spicers Creek catchment is due to the presence of geological structures. These groundwater seepage zones act as mixing zones for rainfall recharge and deeper groundwaters. The main sources of salt to the seepage zones are from deeper Na(Mg)-Cl-rich groundwaters and rainfall accession. The major importance of this research highlights the need for an integrated approach for the use of various geoscientific techniques in dryland salinity research within geologically complex environments.

[No Abstract]

Geostatistical methods were used to find efficient and accurate means for salinity assessment using regionalized random variables and limited sampling. The random variables selected, sodium absorption ratio (SAR), electrical conductivity (EC), and clay content were measured on samples taken over an area of fifteen square miles. Ordinary kriging and co-kriging were used as linear estimators. They were compared on the basis of average kriging variance and sum of squares for error between observed and estimated values. The results indicate a significant improvement in the average kriging variance and sum of squares by using co-kriging estimators. EC was used to estimate SAR because of the high correlation between them. This was not true for clay content. A saving of two-thirds of the cost and time was achieved by using electrical conductivity as an auxiliary variable to estimate sodium absorption ratio. The nonlinear estimator, disjunctive kriging, was an improvement over co-kriging in terms of the variances. More information at the estimation site is a more important consideration than when the estimator is linear. Disjunctive kriging was used to produce an estimate of the conditional probability that the value at an unsampled location is greater than an arbitrary cutoff level. This feature of disjunctive kriging aids salinity assessment and reclamation management. A solute transport model was used to show how saptially variable initial conditions influenced the amount of water required to reclaim a saline soil at each sampling point in a simulated leaching of the area. / Graduation date: 1992

Spicers Creek catchment is located approximately 400 km west of Sydney in the Central West region of New South Wales, Australia. Dryland salinity has been recognised as a major environmental issue impacting soil and water resources in the Central West region of NSW for over 70 years. Due to the geological complexity of the catchment and the presence of high salt loads contained within the soils, groundwater and surface waters, the Spicers Creek catchment was identified as a large contributor of salinity to the Macquarie River catchment. Over fifty-two dryland salinity occurrences have been identified in the Spicers Creek catchment and it appears that dryland salinity is controlled by the presence of geological structures and permeability contrasts in the shallow aquifer system. Combinations of climatic, geological and agricultural factors are escalating salinity problems in the catchment. The main aim of this thesis was to identify the factors affecting salinisation processes in the Spicers Creek catchment. These include the role of geological structures, the source(s) of salts to the groundwater system and the geochemical processes influencing seepage zone development. To achieve these aims a multidisciplinary approach was untaken to understand the soils, geology, hydrogeology and hydrogeochemistry of the catchment. Investigative techniques employed in this project include the use of geophysics, soil chemistry, soil spectroscopy, hydrogeochemistry and environmental isotopes. Evaluation of high-resolution airborne magnetics data showed a major north-east to south-west trending shear zone. This structure dissects the catchment and several other minor faults were observed to be splays off this major structure. These structures were found to be conducive to groundwater flow and are influencing the groundwater chemistry in the fractured aquifer system. Two distinctive groundwater chemical types were identified in the catchment; the saline Na(Mg)-Cl-rich groundwaters associated with the fractured Oakdale Formation and the Na-HCO3-rich groundwaters associated with the intermediate groundwater system. The groundwater chemistry of other deep groundwaters in the catchment appears to be due to mixing between these end-member groundwaters within the fractured bedrock system. The spatial distribution of electrical conductivity, Cl-, Sr2+ and 87Sr/86Sr isotopic ratios showed the correlation between saline groundwaters and the location of faults. Elevated salinities were associated with the location of two crosscutting fault zones. The spatial distribution of HCO3-, K+, Li+ and ?????3CDIC highlighted the extent of Na-HCO3-rich groundwaters in the catchment and showed that these groundwaters are mixing further east than previously envisaged. These findings show that Na(Mg)-Cl-rich groundwaters are geochemically distinctive and have evolved due to extensive water-rock interaction processes within the fracture zones of the Oakdale Formation. These saline groundwaters contain elevated concentrations of trace elements such as As, V and Se, which pose a potential risk for water resources in the area. 87Sr/86Sr isotopic ratios indicated that the source of salinity to the Na(Mg)-Cl-rich groundwaters was not purely from marine or aerosol input. Salt is most likely contributed from various allochthonous and autochthonous sources. This research found that the main mechanism controlling the formation of dryland salinity seepage zones in the Spicers Creek catchment is due to the presence of geological structures. These groundwater seepage zones act as mixing zones for rainfall recharge and deeper groundwaters. The main sources of salt to the seepage zones are from deeper Na(Mg)-Cl-rich groundwaters and rainfall accession. The major importance of this research highlights the need for an integrated approach for the use of various geoscientific techniques in dryland salinity research within geologically complex environments.

Thesis (Ph.D.)--University of Melbourne, Institute of Land and Food Resources, 1999. / Typescript (photocopy). Includes bibliographical references.

Thesis (Ph.D.)--University of Adelaide, School of Mathematical Sciences, Discipline of Applied Mathematics, 2004. / "January 14, 2004" Includes bibliographical references (leaves 201-213). Also available online.