There is a growing need for employing sustainable soil improvement techniques. Concurrently, soil carbon sequestration methods continue to receive more attention in an attempt to reduce greenhouse gas levels contributing to climate change. Exploring the use of gasifier biochar for soil improvement can possibility address these two needs simultaneously. This study investigates the effect of gasifier biochar amendment on mechanical, chemical and hydraulic properties of a local clay with poor engineering properties. Specifically, strength, swelling, compressibility, collapsibility, permeability, water retention, cation exchange capacity, pH, and microstructural characteristics were determined for the clay amended with 5, 10, and 20% biochar. Two sizes of biochar were used. The results showed that biochar amendment improves the strength, swelling potential, permeability, and water retention properties of the clay. Findings suggest that biochar amendment offers a sustainable solution for improving geotechnical properties of marginal soils while providing an efficient method for biospheric carbon sequestration.

Sustaining the global population depends upon modern agricultural practices reliant on large inputs of nitrogen (N) fertilizer, but export of excess N from agroecosystems has negative environmental consequences, such as accelerated eutrophication and associated water quality degradation. The challenges posed by diffuse and widespread nutrient pollution in agricultural drainage waters necessitate cost-effective, adaptable, and reliable solutions. In this context, enhanced denitrification approaches developed over the last several decades have produced denitrifying bioreactors that harness the ability of ubiquitous soil microorganisms to convert bioavailable N into inert N gas, thereby removing bioavailable N from an ecosystem. Denitrifying bioreactors are edge-of-field structures that consist of organic carbon substrate and support the activity of denitrifying soil bacteria that remove N from intercepted nutrient-enriched drainage waters. The potential to improve bioreactor performance and expand their application beyond the Midwest to the agriculturally significant Mid-Atlantic region was investigated with a three-pronged approach: 1) a pilot study investigating controls on N removal, 2) a laboratory study investigating controls on emission of greenhouse gases nitrous oxide (N2O), methane (CH4), and carbon dioxide (CO2), and 3) a field study of one of the first denitrifying bioreactors implemented in the Atlantic Coastal Plain. The pilot and laboratory studies tested the effect of amending woodchip bioreactors with biochar, an organic carbon pyrolysis product demonstrated to enhance microbial activity. The pilot-scale study provides evidence that either hardwood- of softwood-feedstock biochar may increase N removal in woodchip bioreactors, particularly under higher N loading. The results from the laboratory experiment suggest the particular pine-feedstock biochar tested may induce greater greenhouse gas emissions, particularly of the intermediate product of denitrification and potent GHG nitrous oxide. The field study evaluated performance of a biochar-amended woodchip bioreactor installed on a working farm. Two years of monitoring data demonstrated that the bioreactor successfully removed N from drainage waters, but at relatively low rates constrained by low N loading that occurred in the absence of fertilizer application during continuous soy cropping at the site (10.0 kg NO3--N ha-1 yr-1 or 4.86 g NO3- -N m-3 d-1 on the basis of bed volume reached the bioreactor.) Removal rates averaged 0.41 g m-3 d-1 (8.6% removal efficiency), significantly lower than average rates in systems receiving greater N loading in the Midwest, and more similar to installations in the Maryland Coastal Plain. Greenhouse gas fluxes were within the range reported for other bioreactors, and of the N removed an average of only 0.16% was emitted from the bed surface as N2O. This case study provides useful measurements of bioreactor operation under low N loading that informs the boundaries of bioreactor utility, and may have particular regional relevance. The pilot and field studies suggest that wood-based biochars may enhance N removal and may not produce problematic quantities of greenhouse gases, respectively. However, the laboratory study raises the need for caution when considering the costs and benefits amending woodchip bioreactors with biochar and accounting for the effect on greenhouse gas emissions in this calculation, because the tested pine biochar significantly increased these emissions. / PHD

Biochar amendment to agricultural soils has been promoted for use in agricultural systems, both to mitigate global warming by increasing long-term soil carbon (C) sequestration and to enhance soil fertility and crop productivity. The objective of this study was to evaluate the effects of a single biochar application from peanut shell (Arachis hypogea L.) and mixed pine (Pinus spp.) wood to a Typic Hapludults in Blacksburg (VA, USA) and from peanut shell and eucalyptus (Eucalyptus camaldulensis) wood to a tropical, sandy, salt-affected soil in Ndoff (Fatick, Senegal) at 0, 10, and 20 Mg ha⁻¹ on soil chemical properties, inorganic nitrogen supply, and pearl millet production responses under field conditions for two growing seasons (2014 and 2015). Biochar application to temperate soils (Blacksburg) significantly increased total soil carbon, nitrogen, and plant available potassium in both years. In addition, pearl millet yields significant increased (53%) at the 20 Mg ha⁻¹ rate of peanut shell biochar in 2014 but did not persist in year 2. Beneficial effects largely appeared due to nutrient additions. Biochar treatment to tropical, sandy, salt-affected soils (Ndoff) had no effect on soil chemical properties. These results suggest that biochar application could improve soil fertility and crop productivity in temperate soils but had limited effects on tropical, sandy, salt-stressed soils in this study. The disparate results between these two field studies could be explained by differences in soil properties and climate, biomass feedstock, pyrolysis processes, and biochar handling, as well as experimental set-up. / Master of Science

Pharmaceuticals and personal care products found in the environment pose a significant hazard to human and ecosystem health. While there has been significant work on the fate and remediation of pharmaceuticals and personal care products in wastewater treatment, relatively little work has explored the fate, transport and remediation of these compounds in non-point source input. This is concerning given the increasing use of pharmaceuticals in livestock production and wastewater treatment derived biosolids frequently applied to land. These experiments aimed to quantify the abiotic adsorption and biotic transformation and uptake potential of woodchips and biochar-amended woodchips as a potential sorbent strategy for diffuse acetaminophen (ACT) pollution. Batch reactions were created in triplicate, supplied with 5 mM ACT, and analyzed over an eight hr period using ultraviolet spectrophotometry (298 nm). Ultraviolet absorbance readings for each time step then were compared to standard curves and solution ACT concentration was determined. Decreases in ACT from initial concentrations were the result of either abiotic and/or biotic. Overall, the woodchips and biochar-amended woodchips showed similar removal efficiency (16-21% of initial concentration). Whole model ANOVA analysis showed biologic activity having no significant effect on ACT solution concentration. However, within group ANOVA comparison showed significant differences between abiotic and biotic WC and abiotic and biotic WC treatments (controlling for media). Thus, the media effect could have masked the effect of biology on ACT removal. Species capable of degrading ACT exist and further study into their ability to grow and survive on these sorbents requires further work. / Master of Science

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Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2018-04-26T10:41:11Z No. of bitstreams: 2 Tese - Lara Cristina Pereira da Silva Pacheco - 2017.pdf: 3161074 bytes, checksum: 69afc236d4b1540e17072504bc7db6b9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-04-26T11:21:24Z (GMT) No. of bitstreams: 2 Tese - Lara Cristina Pereira da Silva Pacheco - 2017.pdf: 3161074 bytes, checksum: 69afc236d4b1540e17072504bc7db6b9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-04-26T11:21:24Z (GMT). No. of bitstreams: 2 Tese - Lara Cristina Pereira da Silva Pacheco - 2017.pdf: 3161074 bytes, checksum: 69afc236d4b1540e17072504bc7db6b9 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2017-06-29 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / The behavior of the herbicides in the environment is not determined solely by the physicochemical characteristics of the products (pKa, Kow, vapor pressure, water solubility and etc.). Soil attributes (CTC, organic matter, texture, mineralogy, pH, etc.), environmental factors (temperature, rainfall, winds) and the practices adopted in the production systems (cropping system, vegetation cover, chemical fertilization Or organic) also affect the behavior of herbicides in the environment. The objective of this work was to evaluate: 1 - The effect of the soil type on the activity of the herbicides clomazone, diclosulam, oxyfluorfen and sulfentrazone and to determine the ideal dose of this herbicide in each type of soil, through dose- answer; 2 - The activity of the herbicide Oxyfluorfen in soil with addition of biochar of sewage sludge; 3 - The activity of pre-emergent herbicides, in the absence and presence of Pennisetum glaucum straw. The soil type affected the the herbicides activities and, therefore, should be considered when deciding the herbicide applied doses. In Cerrado soils CEC is the most suitable soil attribute to predict the ideal herbicides doses of oxyfluorfen. The addition of biochar from sewage sludge obtained by pyrolysis at 500 ° C increased the sorption of the herbicide Oxyfluorfen to the soil, reducing its availability to the plants. The herbicide efficacy of the herbicides atrazine, clomazone and diclosulam is negatively affected by the presence of straw of Pennisetum glaucum. The presence of straw of Pennisetum glaucum does not affect the effectiveness of the herbicides Oxyfluorfen and Sulfentrazone. / O comportamento dos herbicidas no ambiente não é determinado, somente, pelas características físico-químicas dos produtos (pKa, Kow, pressão de vapor, solubilidade em água e etc). Os atributos do solo (CTC, teor de matéria orgânica, textura, mineralogia, pH, etc), os fatores ambientais (temperatura, precipitação pluviométrica, ventos) e as práticas adotadas nos sistemas de produção (sistema de cultivo, cobertura vegetal, adubação química ou orgânica) também afetam o comportamento dos herbicidas no ambiente. Diante disso, objetivou-se com este trabalho avaliar: 1 – O efeito do tipo de solo na atividade dos herbicidas clomazone, diclosulam, oxyfluorfen e sulfentrazone e determinar a dose ideal desse herbicida em cada tipo de solo, por meio de curvas de dose-resposta; 2 – A atividade do herbicida Oxyfluorfen em solo com adição de biochar de lodo de esgoto; 3 – A atividade de herbicidas pré-emergentes, na ausência e presença de palhada de Pennisetum glaucum. O tipo de solo afeta a atividade dos herbicidas estudados e, portanto, deve ser considerado quando da tomada de decisão das doses aplicadas dos herbicidas. Nos solos de Cerrado, a CTC é o atributo do solo mais indicado para predição das doses a serem aplicadas do herbicida oxyfluorfen. Quanto ao impacto de resíduos orgânicos na atividade de herbicidas, a adição de biochar de lodo de esgosto, obtido pela pirólise a 500°C, aumentou a sorção do herbicida Oxyfluorfen ao solo, reduzindo sua disponibilidade às plantas. A eficácia no controle de plantas daninhas dos herbicidas atrazina, clomazone e diclosulam, éafetada negativamente pela presença de palhada de Pennisetum glaucum. A presença de palhada de Pennisetum glaucum não afeta a eficácia dos herbicidas Oxyfluorfen e Sulfentrazone.

La production de biochars et hydrochars permet de former des amendements enrichis en carbone aromatique, potentiellement plus récalcitrant contre les dégradations dans le sol, tout en produisant massivement des énergies renouvelables. Ces amendements ont pour objectif d’augmenter la quantité de matières organiques des sols (MOS), ainsi que leur fertilité. Néanmoins, due à la diversité des biomasses pouvant être utilisé et des procédés de production, des incompréhensions existent sur le potentiel de ces matériaux à stocker du C dans le sol, à court et à long terme. De plus, des méthodes permettant d’évaluer rapidement la stabilité à long terme de ces matériaux restent à mettre au point, afin de permettre aux utilisateurs de statuer de la qualité de ces nouveaux amendements. Ces travaux ont consisté à évaluer la stabilité de biochars et hydrochars, biologiquement par des incubations de sols, et chimiquement par des oxydations à l’acide dichromate. Les biochars ont montré un haut niveau de stabilité biologique et chimique, permettant de stocker une quantité importante de carbone à l’échelle du siècle. De façon contrastée, les hydrochars se sont caractérisés par une stabilité beaucoup plus faible que les biochars, ne permettant probablement pas de séquestrer massivement du carbone au-delà de la décennie. L’hydrochar a induit un priming effect positif (stimulation), alors que le biochar a induit un priming effect négatif (protection). L’altération physique des deux matériaux a conduit à une augmentation de la stabilité et à une diminution du priming effect, mettant en lumière l’importance des paramètres environnementaux dans les stratégies de séquestration de carbone du sol. Les sols d’anciennes charbonnières ont été utilisés comme modèle d’étude à long terme de l’effet d’un apport de biochar après plusieurs siècles. Leur analyse a mis en évidence que l’apport de biochar améliore durablement les propriétés physicochimiques du sol, telle que la teneur en argile, la capacité d’échange cationique (CEC), la quantité de carbone soluble, et les teneurs en azote et phosphore. Toutefois, après plusieurs siècles d’un amendement de biochar, les communautés microbiennes ne présentaient pas d’adaptation spécifique à la dégradation d’un nouvel apport de biochar. Dans ce modèle, l’apport de résidus de plante a entrainé un priming effect négatif. Ainsi, l’apport de biochar, en générant des conditions particulières, permet le maintient de communautés de microorganismes avec la capacité de réorienter leur métabolisme, afin de dégrader spécifiquement de nouveaux substrats plus facilement minéralisables. D’autres travaux seront nécessaires afin d’évaluer la stabilité des biochars dans le système sol-plante. / Biochars and hydrochars production can form amendments enriched in aromatic carbon, potentially recalcitrant against microbial degradation, while massively producing renewable energy. These amendments are aimed to increase soil organic matter (SOM) quantity, and soil fertility. However, due to the diversity of their feedstock and production processes, misunderstandings exist on the potential of these materials to store C in soil at short and long term. In addition, methods to rapidly evaluate the long-term stability of these materials remain to be developed, in order to allow users to determine the quality of these new amendments. This work was consisted for assessing the stability of biochar and hydrochars, biologically by soil incubations, and chemically by oxidation with acid dichromate. The biochar showed a high level of biological and chemical stability, allowing to storage a large amount of carbon throughout the century. In opposite, the hydrochars might not allow sequestering massively carbon beyond the decade, due to its lower biological and chemical stability. The hydrochars induced a positive priming effect (stimulation) while biochar induced a negative priming effect (protection). Physical weathering of both materials led to an increase of stability and a decrease of the priming effect, highlighting the importance of environmental factors in evaluation of strategies for sequestering carbon. Charcoal kiln soils were used as a model for long-term study of the input of biochar in soil after several centuries. Their analysis showed that the contribution of biochar sustainably improves the physicochemical properties of the soil, such as clay content, cation exchange capacity (CEC), amount of nitrogen, phosphorus, and soluble carbon. However, after several centuries of biochar amendment, microbial communities showed no specific adaptation to the degradation of a new biochar input. In this soil model, the input of plant residues resulted in a negative priming effect. Thus, the contribution of biochar in generating specific conditions, allows the maintenance of microbial communities with the ability to switch of substrates, for a new source of substrates more easily degradable. Further works are needed to assess the stability of biochar in soil-plant system.

Les biochars sont au cœur de la lutte contre les changements globaux. Ils constituent aussi un enjeu pour la gestion durable des sols contaminés. Ces travaux ont été conduits afin de mieux comprendre les effets du biochar sur la mobilité des métaux dans les sols et leur transfert vers les plantes. Une série d’expériences de complexité croissante ont été conduites, impliquant un biochar obtenu par pyrolyse de bois à 450 °C, et deux sols, l’un acide et l’autre alcalin, contaminés par Cd, Pb et Zn suite à l'activité d'une fonderie. Une gamme d’espèces végétales aux réponses contrastées vis-à-vis des métaux a été testée. Des essais de sorption en batch et de lixiviation en colonnes couplés à une caractérisation microscopique et spectroscopique du biochar ont été réalisés, ainsi que des expériences de croissance végétale en vases de végétation, en rhizotrons et en lysimètres. Les résultats démontrent que les phases minérales carbonatées du biochar jouent un rôle prépondérant dans l'immobilisation des métaux. Elles interviennent dans la sorption directe des métaux à la surface du biochar par co-précipitation. Leur dissolution contribue également à l'augmentation du pH du sol, conduisant à une rétention accrue des métaux à la surface des particules du sol. Le biochar modifie le transfert des métaux vers la plante en diminuant la disponibilité des métaux, mais également en diminuant la mobilité de cations majeurs et en modifiant la surface racinaire développée par la plante. Une diminution du transfert du métal vers les parties aériennes de la plante a généralement été observée avec Lolium perenne ou Zea mays, alors qu'une augmentation du prélèvement de Cd et Zn par l'hyperaccumulateur Noccaea caerulescens a été mise en évidence. En conclusion, le biochar contrôle la mobilité des métaux dans les systèmes sol-plante grâce à une série de mécanismes différents. Au plan pratique, le biochar favorise les stratégies de phytostabilisation et de phytoextraction des métaux dans les sols contaminés / Biochars play a central part in the mitigation of global changes. They also represent a challenge for the sustainable management of contaminated soils. This work was conducted in order to better understand the effects of biochar on the mobility of metals in soils and their uptake by plants. A range of experiments was set up following a gradual increase of complexity, with a wood-derived biochar obtained by pyrolysis at 450 °C and two soils, acidic or alkaline, contaminated by Cd, Pb and Zn from smelter activity. Various plant species with contrasting response to metals were tested. Batch sorption and column leaching experiments coupled to microscopic and spectroscopic characterization of biochars were conducted, together with plant growth experiment in pots, rhizoboxes and lysimeters. Results demonstrate that biochar's carbonated mineral phases play a dominant role in the immobilization of metals. They lead to metals direct sorption on the surface of biochar by co-precipitation. Their dissolution also contributes to the increase of soil pH, leading to an increased retention of metals on soil particles. Biochar alters the transfer of metals to the plants by decreasing the availability of metals, but also by decreasing the mobility of major cations and by modifying root surface. A decrease of metal transfer to the shoots was generally observed with Lolium perenne or Zea mays, while an increase of the uptake of Cd and Zn by the hyperaccumulator Noccaea caerulescens was evidenced. In conclusion, biochar controls the mobility of metals in soil-plant systems through a range of different mechanisms. From a practical point of view, biochar promotes both strategies of phytostabilization and phytoextraction of metals in contaminated soils

Water polluted by pharmaceuticals, metals, and phosphates can be hazardous to both the environment and human health. The main aim of this study is to develop low cost, green adsorbents for removal of these pollutants from aqueous solution as a low cost alternative to activated carbon. Biochar was produced from the fast pyrolysis of Douglas fir. Magnetic biochar was prepared by magnetite (Fe3O4) precipitation onto the biochar’s surface from an aqueous Fe3+/Fe2+ solution upon NaOH treatment. Both Douglas fir and magnetic Douglas fir biochars have high uptake and adsorption capacity. Chapter I provides an overview of different biochar production techniques and modification methods. Chapter II is a study of the aqueous adsorption of pharmaceutical products, 4-nitroaniline (4NA), salicylic acid (SA), benzoic acid (BA) and phthalic acid (PA) using Douglas fir and magnetic Douglas fir biochar. The surface chemistry and composition of the magnetic biochar were examined by SEM, SEM-EDX, TEM, PZC, XPS, XRD, elemental analysis, and surface area measurements. Chapter III describes the removal of lead and cadmium using both magnetic and nonmagnetic Douglas fir biochar and Chapter IV describes the removal of phosphate from waste water. In Chapter V, this low cost adsorbent (magnetic Douglas fir biochar) was introduced into an undergraduate laboratory to expose students to water quality issues and methods of contaminant removal enhancing their understanding of these important environmental issues. This experiment introduces new and interesting approaches to water purification as well as deepens the student’s understanding of present environmental concerns regarding pharmaceutical contaminants in wastewater.

Molybdenum (Mo) is a naturally occurring trace element that is present in drinking water mostly in the molybdate (MoO42-) form in well water. Recently, the EPA deemed Mo as a potential contaminant because exposure can lead to health effects such as gout, hyperuricemia, and lung cancer. In this work, we have assessed the sorptive removal of Mo using Douglas fir biochar (DFBC) and its chemically-coprecipitated iron oxide analogue (DFMBC). Adsorption was studied varying the batch sorption conditions; pH, equilibrium time (5 min-24 h), initial Mo concentrations (2.5-1000 mg/L), temperatures (5, 25, and 40 °C) and equilibrium method. Langmuir capacities for DFBC and DFMBC (at pH 3, 2 h equilibrium) were in 359.3-487.9 mg/g and 288.3-571.9 mg/g range, respectively. Adsorbents and Mo-laden adsorbents were characterized by elemental analysis, BET, PZC, SEM, TEM, EDS, XRD, and XPS. These data suggest that DFBC and DFMBC can be potential candidates for Mo sorption.