Made available in DSpace on 2016-06-02T18:55:22Z (GMT). No. of bitstreams: 1 4143.pdf: 4028323 bytes, checksum: bb244562f3f5e6280f0390dc28f2aec5 (MD5) Previous issue date: 2011-02-23 / Universidade Federal de Sao Carlos / The Restinga forest is a set of plant communities in mosaic, determined by the characteristics of their substrates as a result of depositional processes and ages. And of all the ecosystems associated with the Atlantic, the most fragile and susceptible to human disturbance. In this complex mosaic are the physiognomies of restinga forests of high-stage regeneration (high restinga) and middle stage of regeneration (low restinga), each with its plant characteristics that differentiate them. Located on the coastal plains of the Brazilian coast, suffering internal influences both the continental slopes, as well as navy. His solo comes from the Quaternary and are subject to constant deposition of sediments. The climate on the coast, according to Köppen classification, type is tropical. In recent decades, with growing concern about natural resources and environmental quality, intensified research, resulting in the definition of soil quality (SQ), strongly rooted in the concept of sustainability. To this end, several models have been proposed in an attempt to assess soil quality index (SQI). The monitoring of soil quality should be directed to detect trends that are measurable changes in a period of time. The objectives of this study were: a) Comparative evaluation of the characterization of soil fertility, through chemical and physical parameters under restinga forest of high and low, with respect to distribution of the root in the soil profile, and b) Determine the index Soil Quality for restinga forest in high-and middle-stage regeneration and a resting area with no vegetation. This work was conducted in four locations: (1) Anchieta Island, Ubatuba, (2) Juréia-Itatins Ecological Station, Iguape, (3) Vila das Pedrinhas, Comprida Island; and (4) Cardoso Island, Cananeia. Studies on soil fertility have been made in depths of 0 to 5, 00-10, 00-20, 20-40 and 40 to 60cm for the chemical and physical analysis, with five replicates for each vegetation type, for each study site, each composed of twelve subsamples. Also being evaluated the distribution of the root in the soil profile. To determine the rate of soil quality, chemical analysis were made, microbiological and physical-layer 0-10cm depth. Using two models in determining the rate of soil quality: Additive Model (MA) and Comparative Additive Model (MAC). It is concluded that the root system for all studied vegetation types found in the more superficial layers, 0-10 and 10-20cm, mainly in the 0-10cm (80%), that low levels of calcium and elevated aluminum restrict root development. All the studied have low soil fertility, with base saturation values below 16%, where most of these environments CEC is occupied by aluminum. The additive model produces quantitative results and the additive model comparative quantitative and qualitative results (ground potential), the SQI values were obtained by the MAC for all local and low vegetation types and realistic, demonstrating the low potential for biomass production in these soils, and its low resilience. Values similar to the forests with and without vegetation showed numerically the consideration that the restinga is an edaphic vegetation. And that the use of routine chemical analysis is sufficient to determine the IQS. / A Restinga é um conjunto de comunidades vegetais em mosaico, determinadas pelas características de seus substratos resultantes de processos deposicionais e idades. De todos os ecossistemas associados à Mata Atlântica, a restinga é a mais frágil e susceptível às perturbações antrópicas. Neste complexo mosaico encontram-se as fitofisionomias de florestas de restinga em estágio de elevada regeneração (restinga alta) e em estágio de média regeneração (restinga baixa), cada qual com suas características vegetais que as diferenciam. Localizam-se nas planícies costeiras do litoral brasileiro, sofrendo influência tanto das encostas internas continentais, bem como marinha. Seu solo tem origem no quaternário e estão sujeitos a constantes deposição de sedimentos. O clima no litoral, segundo classificação de Köppen, é do tipo tropical. Nas últimas décadas, com a crescente preocupação com os recursos naturais e a qualidade do meio ambiente, intensificaram-se as pesquisas, resultando na definição do conceito de Qualidade do Solo (QS), fortemente alicerçado no conceito de sustentabilidade. Para tanto, vários modelos foram propostos na tentativa de avaliar um Índice de Qualidade do Solo (IQS). O monitoramento da qualidade do solo deve ser orientado para detectar tendências de mudanças que são mensuráveis num período de tempo. Os Objetivos deste estudo foram: a) avaliação comparativa da caracterização da fertilidade do solo, através dos parâmetros químicos e físicos, sob floresta de restinga alta e baixa, com relação a distribuição do sistema radicular no perfil do solo; e b) determinar o Índice de Qualidade do Solo para floresta de restinga em estágio de elevada e média regeneração e para uma área de restinga sem vegetação. Este estudo foi realizado em quatro locais: (1) Parque Estadual da Ilha Anchieta, município de Ubatuba; (2) Estação Ecológica Juréia-Itatins, Estação Ecológica dos Chauás, município de Iguape; (3) Vila de Pedrinhas no município de Ilha Comprida; e (4) Parque Estadual da Ilha do Cardoso, município de Cananéia. Os estudos sobre fertilidade do solo foram feitos nas profundidades de 0 a 5, 0 a 10, 0 a 20, 20 a 40 e 40 a 60cm para as análises químicas e físicas, com cinco repetições para cada fitofisionomia, para cada local de estudo, cada uma delas composta por doze subamostras. Também foi avaliada a distribuição do sistema radicular no perfil do solo. Para a determinação do índice de qualidade do solo (IQS), foram feitas analises químicas, físicas e microbiológicas na camada de 0-10cm de profundidade. Utilizaram-se dois modelos na determinação do índice de qualidade do solo: Modelo Aditivo (MA) e Modelo Aditivo Comparativo (MAC). Conclui-se que o sistema radicular para todas as fitofisionomias estudadas encontra-se nas camadas mais superficiais, 0-10 e 10-20cm, principalmente na camada de 0-10cm (80%), e que os teores baixos de cálcio e elevados de alumínio restringem o desenvolvimento radicular. Todos os ambientes estudados apresentaram baixa fertilidade do solo, com valores de saturação por bases inferiores a 18%, onde a maior parte da CTC destes ambientes está ocupada por alumínio. O modelo aditivo produz resultados quantitativos e o modelo aditivo comparativo resultados quantitativos e qualitativos (potencial do solo), que os valores de IQS obtidos pelo MAC foram baixos e realísticos para todos os locais e fitofisionomias, demonstrando o baixo potencial de produção de biomassa desses solos, bem como sua baixa resiliência. Os valores semelhantes para as florestas com e sem vegetação demonstraram que a restinga é uma vegetação edáfica, e que o emprego de análise química de rotina é suficiente na determinação do índice de qualidade do solo.

Les minéraux argileux gonflants sont omniprésents dans tous les compartiments de la surface de la Terre et notamment dans les sols. La structure lamellaire de ces minéraux et leur faible taille leur confèrent une forte réactivité notamment vis à vis des polluants et nutriments qui sont présents dans les eaux porales des sols. Dans ce cadre, cette thèse vise à contribuer à une meilleure compréhension des interactions entre des minéraux argileux gonflants et des cations nutritifs (calcium, strontium) et/ou d'intérêt environnemental (césium). Dans les sols, ces minéraux possèdent de larges distributions de taille et de cristallochimie (charge des feuillets). Par conséquent, pour mieux comprendre le rôle de chacun de ces paramètres sur la réactivité de ces particules naturelles, nous avons travaillé avec des « systèmes modèles », représentatifs des particules argileuses des sols : des particules de vermiculite triées en taille et des saponites synthétiques avec des charges de feuillets contrôlées. Les résultats d'adsorption des cations étudiés (Cs, Sr) en compétition avec les cations majeurs des eaux naturelles (Na, Ca) ont été obtenus en couplant l'analyse chimique des solutions et la modélisation des réflexions 00ℓ des diffractogrammes de rayons X afin d'obtenir la distribution de cations entre les différents sites d'adsorption (interfoliaire vs externes). Une telle approche et l'utilisation des « systèmes modèles » nous ont permis d'obtenir des paramètres quantitatifs décrivant la réactivité des minéraux argileux gonflants des sols. Ces paramètres pourront être pris en compte dans les codes de transport prédisant la migration des cations dans les sols. / The swelling clay minerals are ubiquitous in all areas of the surface of the Earth, particularly in soils. The lamellar structure of these minerals and their small size are at the origin of their high reactivity in particular with respect to pollutants and nutrients that are present in soil pore water. In this context, our work aims to contribute to a better understanding of the interactions between swelling clay minerals and cations of nutritive (calcium) and/or environmental interest (cesium, strontium). In soils, swelling clay minerals have broad size distribution and can have a varied crystal chemistry. Therefore, to better understand the role of each of these parameters on the reactivity of the natural particles, we worked with "model systems", which are yet representative of the swelling clay particles encountered in soil environment. Different particle size fractions of vermiculite and different synthetic saponites characterised by well-controlled layer charge were used as "model systems". Results concerning ion-exchange isotherms for Cs and Sr, in competition with major cations of natural waters (Na, Ca), were obtained by combining chemical analyses and 00ℓ reflection modelling of X-ray diffractograms in order to assess the cation distribution between the different adsorption sites (interlayer vs external) located on swelling clay minerals. Such approach and the use of ‘model systems’ have allowed us to obtain quantitative parameters describing the reactivity of soil swelling clay mineral particles, and should be considered in reactive transport codes devoted to predict the migration of nutritive and polluted cations in soil environments.

The aim of this master thesis is study of possibilities of processing energy by-products, especially coal fly ash and fluidized bed ash, by hydrothermal treatment. Thanks to hydrothermal conditions and proper alkali activation of ashes we can obtain zeolites. Zeolites are microporous crystalline aluminosilicates which are use in many industrial sectors as catalysts, adsorbents and very good ion exchangers. The results of hydrothermal synthesis are influenced by many variable factors. This thesis mainly focused on influence of chosen alkali activator and the concentration of the activator together with a temperature of hydrothermal process. Other factor that is studied is choice of starting materials and solution/ash ratio. Phase composition of prepared samples was characterized by XRD and scanning electron microscopy (SEM). Also cation exchange capacity of prepared samples was determined.

>Magister Scientiae - MSc / Millions of tonnes of fly ash are generated worldwide every year to satisfy the large demand for energy. Management of this fly ash has been a concern and various approaches for its beneficial use have been investigated. Over the last two decades, there has been intensive research internationally that has focused on the use of different sources of fly ash for zeolite synthesis.However, most of the studies have concentrated on class C fly ash and very few have reported the use of South African class F fly ash as feedstock for zeolite synthesis.Class F fly ash from South Africa has been confirmed to be a good substrate for zeolite synthesis due to its compositional dominance of aluminosilicate and silicate phases. However, because differences in quartz-mullite/glass proportions of fly ash from different sources produces impure phases or different zeolite mineral phases under the same activation conditions, the present study focused on optimization of synthesis conditions to obtain pure phase zeolite Na-P1 from class F South African coal fly ash. Synthesis variables evaluated in this study were; hydrothermal treatment time (12 - 48 hours), temperature (100 – 160 oC) and addition of varying molar quantities of water during the hydrothermal treatment step (H2O:SiO2 molar ratio ranged between 0 - 0.49).Once the most suitable conditions for the synthesis of pure phase zeolite Na-P1 from fly ash were identified, a statistical approach was adopted to refine the experiments, that was designed to evaluate the interactive effects of some of the most important synthesis variables. In this case, the four synthesis variables; NaOH concentration (NaOH: SiO2 molar ratio ranged between 0.35– 0.71), ageing temperature (35 oC – 55 oC), hydrothermal treatment time (36 - 60 hours) and temperature (130 oC – 150 oC) were studied. The response was determined by evaluating the improvement in the cation exchange capacity of the product zeolite.The starting materials (fly ashes from Arnot, Hendrina and Duvha power stations) and the synthesized zeolite product were characterized chemically, mineralogically and morphologically by X-Ray fluorescence spectrometry, X-ray powder diffraction, scanning electron microscopy, and transmission electron microscopy. Other characterization technique used in the study were Fourier transform infrared spectroscopy to provide structural information and also monitor evolution of crystallinity during synthesis, as well as cation exchange capacity to determine the amount of exchangeable positively charged ions. Nitrogen adsorption was used to determine the surface area and porosity, and inductively coupled mass spectrometry for multi-elemental analysis of the post-synthesis supernatants.The results from the X-ray diffraction spectroscopy showed that the most pure zeolite Na-P1 phase was achieved when the molar regime was 1 SiO2 : 0.36 Al2O3 : 0.59 NaOH : 0.49 H2O and at synthesis conditions such that ageing was done at 47 oC for 48 hours while the hydrothermal treatment time and temperature was held at 48 hours and 140 oC, respectively. Results from statistically designed experiments show that there was a distinct variation of phase purity with synthesis conditions. From the analysis of linear and non linear interactions, it was found that the main effects were ageing temperature and hydrothermal treatment time and temperature, which also showed some interactions. This experimental approach enabled a clearer understanding of the relationship between the synthesis conditions and the purity of the zeolite Na-P1 obtained.The quality of zeolites is a major determinant in the efficiency of toxic element removal from waste water. Preliminary experiments conducted using optimised zeolite Na-P1 obtained in this study with a cation exchange capacity of 4.11 meq/g showed a high percentage removal of Pb,Cd, Ni, Mn, V, As, B, Fe, Se, Mo Sr, Ba and Zn from process brine obtained from Emalahleni water reclamation plant.In summary, a pure phase of zeolite Na-P1 was obtained from South African class F fly ash feedstock at relatively mild temperature. The systematic approach, incorporating statistical design of experiments, developed in this study resulted in a better understanding regarding the relationships of synthesis parameters in the formation of zeolites from fly ash. The zeolite Na-P1 synthesized with a high cation exchange capacity was effective for removal of toxic elements from brine.

Since a large number of polar and often ionizable anthropogenic organic trace compounds, such as pharmaceutical residues, can be detected in various stages of the water cycle, there is a need to elucidate the effects and behavior of such substances in the aquatic environment. Despite the fact that numerous studies on the sorption behavior of ionizable organic trace compounds have already been carried out, reliable sorption models, which allow a sufficiently accurate prediction of the sorption of organic cations, are not yet available. For this reason, the general objective of this thesis was to improve the fundamental process understanding of the interactions between dissolved cationic organic substances and solid surfaces including relevant influence parameters. The investigations were based on a differentiated process consideration in order to ultimately provide the essential prerequisites for a future reliable prediction of the sorption behavior of cationic organic compounds. Due to the complex superposition of several mechanisms, the basic relationships cannot be clearly elucidated with heterogeneous sorbents. Therefore, it was consciously worked with largely homogeneous, synthetic sorbents. The use of well-defined sorbents with different properties as well as the variation of background electrolyte concentration and the targeted use of different sorbates were the 'tools' that were used to identify and to separate the underlying sorption processes. / Da eine Vielzahl polarer und oftmals ionisierbarer anthropogener organischer Spurenstoffe, wie z. B. Pharmakarückstände, in verschiedenen Bereichen des Wasserkreislaufes nachweisbar ist, besteht die Notwendigkeit die Wirkung und das Verhalten solcher Spurenstoffe in der Umwelt näher aufzuklären. Trotz der Tatsache, dass bereits zahlreiche Untersuchungen zum Sorptionsverhalten ionisierbarer organischer Spurenstoffe bestehen, sind zuverlässige prognosefähige Sorptionsmodelle, welche eine ausreichend genaue Vorhersage der Sorption von organischen Kationen ermöglichen, zurzeit noch nicht verfügbar. Das generelle Ziel dieser Arbeit bestand daher darin, das grundlegende Prozessverständnis der Wechselwirkungen zwischen gelösten kationischen organischen Substanzen und festen Oberflächen einschließlich relevanter Einflussgrößen zu verbessern. Die Untersuchungen basierten auf einer differenzierten Prozessbetrachtung, um letztlich die wesentlichen Voraussetzungen für eine zukünftig zuverlässige Prognose des Sorptionsverhaltens kationischer organischer Verbindungen zu liefern. Aufgrund der komplexen Überlagerung mehrerer Mechanismen können die grundlegenden Zusammenhänge mit heterogen zusammengesetzten natürlichen Sorbentien nicht eindeutig aufgeklärt werden. Daher wurde bewusst mit weitgehend homogenen, synthetischen Sorbentien gearbeitet. Die Verwendung wohldefinierter Sorbentien mit unterschiedlichen Eigenschaften sowie die Variation der Elektrolytkonzentration und der gezielte Einsatz verschiedener Sorptive waren die 'Werkzeuge', die verwendet wurden, um die zugrunde liegenden Sorptionsprozesse zu identifizieren und zu separieren.

Världen står inför ett stort vattenförsörjningsproblem som måste lösas – så många som 884 miljoner människor använder idag potentiellt förorenade vattenkällor till sitt dricksvatten. Denna rapport fokuserar på ett av de drabbade länderna som är Uganda. Syftet med projektet är att undersöka vilket/vilka av de fem olika ugandiska växterna; Erythrina abyssinica, Musa spp, Cyperus papyrus, Imperata cylindrica och Coffea canephora som är mest lämplig för rening av kadmium- och blykontaminerat grundvatten. Katjonbyteskapaciteten bestäms genom laboration. Analyser kring växtmaterialen görs med hjälp av litteraturstudier och intervjuer med en doktorand från Uganda. M. spp visar sig ha klart högst katjonbyteskapacitet och finns även i form av mycket avfall, därför anses denna vara det mest lämpliga materialet för rening. Lösningen skulle kunna implementeras i samhället med ett filter gjort av växtmaterial, om vidare forskning görs. / The world is facing a major water supply problem to solve, as many as 884 million people currently use potentially polluted water sources for their drinking water. This report focuses on one of the affected countries, which is Uganda. The project aims to examine which of the five different Ugandan plants; Erythrina abyssinica, Musa spp, Cyperus papyrus, Imperata cylindrica and Coffea canephora that is the most suitable for purification of cadmium- and lead contaminated groundwater. The cation exchange capacity is determined by laboratory experiment. Literature studies and interviews with a Ugandan postgraduate student are used for the analysis of the plant materials. M. spp has the highest cation exchange capacity and contributes with a lot of waste material; therefore it is considered the most suitable material for purification. The solution could be implemented in the community with a filter made of plant material, if further research is done.

Concrete, the second most consumed material on earth after water, is a source of environmental problems due to global urbanization. The production of this construction material requires a large amount of natural resources, and portland cement (PC) is responsible for around 8 % of planet-warming CO2 emissions. Producing 1 ton of PC will release roughly 1 ton of CO2 into the atmosphere. In 2021, around 92 million metric tons of PC were produced in the U.S., and a total of 4.4 billion tons were manufactured worldwide. While there was a yearly increase of around 1.5 % in the direct CO2 intensity of cement production from 2015 to 2021, urgent annual declines of 3 % until 2030 are necessary to be in line with the Net Zero Emissions by 2050 Scenario. This dissertation presents different approaches and technologies to offset the CO2 footprint of the production of cement clinker, concrete, and cementitious materials in general. First, this dissertation investigated the possibility of using end-of-life tire (ELT) rubber powder and its zinc-recovered residual (treated ELT rubber) to partially replace fine aggregates of different construction and infrastructure materials including stabilized soft soil (0 %, 10 %, 30 %, and 50 % ELT rubber added by clay volume), portland cement concrete (0 %, 10 %, 20 %, and 30 % ELT rubber added by sand volume), and asphalt concrete (20 % ELT rubber added by sand volume). This work was discussed through aspects of engineering properties and environmental impacts. The results reveal that the ELT rubber had both negative and positive effects on the engineering properties of the three materials while this waste posed a huge leachability of zinc and total organic carbon (TOC) content when being subjected to aqueous environments. However, the findings indicate that all three materials' matrices could effectively immobilize most leachable zinc from the ELT rubber by more than 90 %. Meanwhile, only stabilized soft soil and asphalt concrete could effectively deal with leachable TOC content from ELT rubber, and portland cement concrete needed the addition of silica fume to reduce TOC concentration in its leachate. Second, while previous studies have shown that steel furnace slag (SFS) can stabilize clay soils, the evidence is not clear if the stabilization mechanism is chemical and/or mechanical. This dissertation used isothermal calorimetry (IC) to quantify the heat of hydration of the mixture to assess the chemical aspects of the stabilization. Specifically, kaolin and bentonite clays were each blended with 40 % SFS by mass at water-to-binder ratios ranging from 1.0 to 1.5. The hydration properties of stabilized mixtures using lime or PC were also tested for comparison at the same experimental conditions. The obtained thermal power and total heat curves of stabilized mixtures confirmed that, for the specific SFS in this study, there is a hydration process taking place in clay stabilized by SFS. Relative to lime and PC, the SFS performed similarly in terms of heat of hydration behavior. When blended into clays, SFS provided a more significant heat of hydration behavior than cement, but that was much milder than lime. X-ray diffraction (XRD) and thermogravimetric analysis (TGA) were also employed to qualitatively analyze the mineralogy of the stabilized mixtures. Finally, this dissertation adopted a Digestion-Titration Method (DTM) for the determination of CO2 content in cementitious materials that has been mineralized in the form of calcium carbonate (CaCO3). This method was modified based on tests that were originally developed in the early 1900s. The method uses hydrochloric acid to digest CaCO3 under vacuum conditions. The CO2 released is captured by a barium hydroxide solution, which is then titrated to quantify the amount of CO2 absorbed. A design of experiments approach was used to optimize the experimental conditions. Samples of known CaCO3 content were first evaluated to establish the baseline test performance, and additional tests were performed on portland cement and various rock samples. The results were also compared to TGA, including a discussion to compare the two test methods. The data suggest that the new test method is feasibly applicable to chemically determine the CO2 captured in cementitious materials, and it can be an alternative method for TGA with lower experimental cost and easier access. Overall, it is evident that cement, concrete, and construction materials are essential to the functionality of civilization. Dealing with CO2 emissions and natural resource depletion induced by the production of these construction materials is urgent for sustainable development. Attempts toward construction materials with lower embodied CO2 by using low-carbon aggregates (e.g., waste aggregates, recycled aggregates) and alternative cementitious binders while controlling the environmental effects of the utilized waste materials are currently viable sustainable approaches. In addition, tools or new test methods that can support measuring the effectiveness of these reduced carbon cementitious materials are necessary. This dissertation investigates the feasibility of the use of ELT rubber waste in construction materials to reduce the exploitation of natural resources considering engineering properties and environmental impacts. It also provides a deeper understanding of the hydration behavior of stabilized soil using SFS which is expected to partially or fully replace PC in the material. Experimentally, it develops a chemical test model as an alternative method for TGA with lower experimental cost, less interference, and easier access to determine the CO2 captured in cementitious materials. / Doctor of Philosophy / Concrete, the second most consumed material on earth after water, is a source of environmental problems due to global urbanization. The production of this construction material requires a large amount of natural resources, and portland cement (PC) is responsible for around 8 % of planet-warming CO2 emissions. This dissertation presents different approaches and technologies to offset the CO2 footprint of the production of construction materials (i.e., cement clinker, concrete, and general cementitious materials). First, this dissertation investigated the possibility of using end-of-life tire (ELT) rubber powder in different construction materials including stabilized soft soil, portland cement concrete, and asphalt concrete. This work was discussed through aspects of engineering properties and environmental impacts. The results reveal that the ELT rubber had both negative and positive effects on the engineering properties of the three materials. In return, all three materials' matrices could effectively immobilize most leachable zinc and total organic carbon (TOC) from the ELT rubber, which are detrimental to aquatic animals, plants, and humans. Second, this dissertation used isothermal calorimetry (IC) for the first time to study the heat of hydration of soil stabilized by steel furnace slag (SFS) to assess the chemical aspects of the stabilization. The work compared the hydration behavior of SFS in clayey soil with traditional stabilizers such as lime or portland cement. The results demonstrated that there were chemical reactions taking place during the hydration of stabilized soil using SFS, explaining the improvement in engineering properties of the stabilized soil. Moreover, this dissertation adopted a Digestion-Titration Method (DTM) for the determination of mineralized CO2 content in cementitious materials. The method uses hydrochloric acid to digest CaCO3 under vacuum conditions. The CO2 released is captured by a barium hydroxide solution, which is then titrated to quantify the amount of CO2 absorbed. The data suggest that the new test method is feasibly applicable to chemically determine the CO2 mineralized in cementitious materials, and it can be an alternative method for thermogravimetric analysis with lower experimental cost and easier access. Overall, it is evident that cement, concrete, and construction materials are essential to the functionality of civilization. Dealing with CO2 emissions and natural resource depletion induced by the production of these construction materials is urgent for sustainable development. This dissertation is expected to fill the knowledge gap in carbon neutral construction materials research, including increasing the use of low-carbon aggregates (e.g., waste aggregates, recycled aggregates) and alternative cementitious binders as well as developing new test methods that can support measuring the effectiveness of these reduced carbon cementitious materials.

Soil characterization provides the basic information necessary for understanding the physical, chemical, and biological properties of soils. Knowledge about soils can in turn be used to inform management practices, optimize agricultural operations, and ensure the continuation of ecosystem services provided by soils. However, current analytical standards for identifying each distinct property are costly and time-consuming. The optimization of laboratory grade technology for wide scale use is demonstrated by advances in a proximal soil sensing technique known as portable X-ray fluorescence spectrometry (pXRF). pXRF analyzers use high energy Xrays that interact with a sample to cause characteristic reflorescence that can be distinguished by the analyzer for its energy and intensity to determine the chemical composition of the sample. While pXRF only measures total elemental abundance, the concentrations of certain elements have been used as a proxy to develop models capable of predicting soil characteristics. This study aimed to evaluate existing models and model building techniques for predicting soil pH, texture, cation exchange capacity (CEC), soil organic carbon (SOC), total nitrogen (TN), and C:N ratio from pXRF spectra and assess their fittingness for California soils by comparing predictions to results from laboratory methods. Multiple linear regression (MLR) and random forest (RF) models were created for each property using a training subset of data and evaluated by R2 , RMSE, RPD and RPIQ on an unseen test set. The California soils sample set was comprised of 480 soil samples from across the state that were subject to laboratory and pXRF analysis in GeoChem mode. Results showed that existing data models applied to the CA soils dataset lacked predictive ability. In comparison, data models generated using MLR with 10-fold cross validation for variable selection improved predictions, while algorithmic modeling produced the best estimates for all properties besides pH. The best models produced for each property gave RMSE values of 0.489 for pH, 10.8 for sand %, 6.06 for clay % (together predicting the correct texture class 74% of the time), 6.79 for CEC (cmolc/kg soil), 1.01 for SOC %, 0.062 for TN %, and 7.02 for C:N ratio. Where R2 and RMSE were observed to fluctuate inconsistently with a change in the random train/test splits, RPD and RPIQ were more stable, which may indicate a more useful representation of out of sample applicability. RF modeling for TN content provided the best predictive model overall (R2 = 0.782, RMSE = 0.062, RPD = 2.041, and RPIQ = 2.96). RF models for CEC and TN % achieved RPD values >2, indicating stable predictive models (Cheng et al., 2021). Lower RPD values between 1.75 and 2 and RPIQ >2 were also found for MLR models of CEC, and TN %, as well as RF models for SOC. Better estimates for chemical properties (CEC, N, SOC) when compared to physical properties (texture), may be attributable to a correlation between elemental signatures and organic matter. All models were improved with the addition of categorical variables (land-use and sample set) but came at a great statistical cost (9 extra predictors). Separating models by land type and lab characterization method revealed some improvements within land types, but these effects could not be fully untangled from sample set. Thus, the consortia of characterizing bodies for ‘true’ lab data may have been a drawback in model performance, by confounding inter-lab errors with predictive errors. Future studies using pXRF analysis for soil property estimation should investigate how predictive v models are affected by characterizing method and lab body. While statewide models for California soils provided what may be an acceptable level of error for some applications, models calibrated for a specific site using consistent lab characterization methods likely provide a higher degree of accuracy for indirect measurements of some key soil properties.

No description available.

Increased water- and fertilizer-use-efficiency in containerized crop production, via reduced water loss, enhances crop-available nutrients while reducing non-point source agrichemical contributions in accordance with regulatory standards. Previous studies detailed nutrient leaching patterns throughout crop production seasons, leaving little known about water and dissolved nutrient (solute) movement through soilless substrates during irrigation. The following experiments evaluated fundamental water and solute transport principles through pine-bark based substrates. 1) Ilex crenata Thunb. 'Bennett's Compactum' were grown in 2.7 L containers. Tensiometers detected wetting front (WF) movement throughout the substrate during irrigation. 2) Tracer solution (containing NO3-, PO43- and K+) and deionized water (DI) were applied to substrate-filled columns to characterize tracer breakthrough under saturated and unsaturated conditions. 3) Controlled-release fertilizer (CRF) was topdressed (surface-applied), incorporated (throughout substrate), dibbled (center of substrate) or not applied to fallow substrate, irrigated with DI and leachate analyzed to determine nutrient concentrations throughout irrigation. Tensiometers revealed that seasonal root growth affected substrate pre-irrigation moisture distribution. Wetting fronts channeled through the substrate before becoming thoroughly wetted. Tracer breakthrough occurred with less effluent volume under unsaturated conditions. Breakthrough of NO3- and PO43- was relatively conservative, though 37% of K+ was retained by the substrate. Leachate concentrations for topdressed and incorporated CRF peaked early (first 50mL effluent) before diminishing with continued leaching. Leachate concentrations for dibbled CRF initially increased (first 150mL leachate), plateaued and then diminished. These results show the relative rapidity which water and solutes move through pine-bark during irrigation and demonstrate methods for future research on within-irrigation solute transport. / Master of Science