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Quaternary ammonium compounds (QACs) are widely used in commercial and consumer applications as disinfectants, fabric softeners, hair conditioners, and emulsifying agents. The massive production and utilization of QACs has led to their extensive discharge into the environment, raising concerns globally. Several studies have reported on potential risks and detrimental effects of QACs on the natural environment and public wastewater treatment plants. Biological treatment has been found to be an effective way to remove QACs and especially aerobic treatment processes can provide rapid biodegradation via a consortium of bacteria. Although extensive research has been conducted on the fate and effect of QACs, relatively little is known about their effect on aerobic biological treatment processes, especially on nitrification. Research was conducted on the fate and effect of alkyl benzyl dimethyl ammonium chloride (AB), a QAC widely used as disinfectant, in mixed aerobic and nitrifying cultures. The results of this study demonstrated that up to 50 mg/L AB was efficiently degraded in a mixed aerobic culture fed with dextrin and peptone, although trace residual AB levels were observed. Nitrification of the produced ammonia was complete at an AB concentration of 20 mg/L after an acclimation period, but was almost completely inhibited at 50 mg/L. Mixed aerobic cultures maintained only with AB as external nitrogen and carbon source achieved a high degree of AB degradation at both 20 and 50 mg/L. Ammonia oxidation by a nitrifying culture, enriched with ammonium chloride and sodium bicarbonate, was inhibited with increasing AB concentration and completely ceased at 15 mg/L AB. Degradation or utilization of AB was not observed for all tested AB concentrations between 2 to 20 mg/L. Based on these experimental results, and assuming non-competitive inhibition, a relatively low value of the AB inhibition coefficient was obtained, which indicates a relatively high susceptibility of the ammonia oxidizers to AB. The results of this study have significant implications for both engineered and natural systems relative to the fate and effect of QACs.

Nitroglycerin (NG) is a toxic explosive commonly found in soil and contaminated groundwater at old manufacturing plants and military ranges. When NG enters an aquifer, it behaves as a dense non-aqueous phase liquid (DNAPL). Nitroglycerin is an impact sensitive explosive and therefore excavating the area to remove or treat the contaminant can be dangerous. In situ bioremediation and natural attenuation of NG have been proposed as remediation alternatives and it is therefore necessary to understand the degradation mechanisms of NG in contaminated soil and groundwater and investigate the potential for using bioremediation at contaminated sites. Many bacteria have been isolated for the ability to transform NG as a source of nitrogen, but no isolates have used NG as a sole source of carbon, nitrogen, and energy. We isolated Arthrobacter JBH1 from NG contaminated soil by selective enrichment with NG as the sole growth substrate. The degradation pathway involves a sequential denitration to 1,2-dinitroglycerin (DNG) and 1-mononitroglycerin (MNG) with simultaneous release of nitrite. Flavoproteins of the Old Yellow Enzyme (OYE) family capable of removing the first and second nitro groups from NG have been studied in the past and we identified an OYE homolog in JBH1 capable of selectively producing the 1 MNG intermediate. To our knowledge, there is no previous report on enzymes capable transforming MNG. Here we show evidence that a glycerol kinase homolog in JBH1 is capable of transforming 1 MNG into 1-nitro-3-phosphoglycerol, which could be later introduced into a widespread pathway, where the last nitro group is removed. Overall, NG is converted to CO2 and biomass and some of the nitrite released during denitration is incorporated into biomass as well. As a result, NG can be now considered a growth substrate, which changes the potential to bioremediate NG contaminated sites. The magnitude of the effect of biodegradation processes in the fate of NG in porous systems was unknown, and we have been able to quantify these effects, determine degradation rates, and have evidence that bioaugmentation with Arthrobacter sp. strain JBH1 could result in complete mineralization in contaminated soil and sediments contaminated with NG, without the addition of other carbon sources. Site specific conditions have the potential to affect NG degradation rates in situ. Experiments were conducted to investigate NG degradation at various pH values and NG concentrations, and the effects of common co-contaminants on NG degradation rates. Arthrobacter JBH1 was capable of growing on NG at pH values as low as 5.1 and NG concentrations as high as 1.2 mM. The presence of explosive co-contaminants at the site such as trinitrotoluene and 2,4-dinitrotoluene lowered NG degradation rates, and could potentially result in NG recalcitrance. Collectively, these results provide the basis for NG bioremediation and natural attenuation at sites contaminated with NG without the addition of other sources of carbon. Nonetheless, careful attention should be paid to site-specific conditions that can affect degradation rates.

This project studied the biodegradation of a plasticizer, di-(2-ethylhexyl) adipate (DEHA), by two mammalian cell lines, HepG2 and WIF-B, in vitro . An MTT assay showed that DEHA had a toxic effect on both cell lines. Despite this, both hepatocyte cell lines successfully degraded the plasticizer. Metabolites were identified and quantified by gas chromatography. HepG2 cells showed minimal alcohol dehydrogense activity and this resulted in the accumulation of 2-ethylhexanol. WIF-B cells were able to breakdown the alcohol and produced 2-ethylhexanoic acid. It is important to note that an enzyme was essential for this step in the degradation of the plasticizer, as this proves that it was biodegradation and not physical degradation. By comparing the metabolites formed and the order of their appearance, the degradation pathway in these mammalian cells was found to be similar to the established degradation pathways for bacteria, fungi and yeast.

Bioremediation is the process whereby the degradation of organic polluting compounds occurs as a result of biochemical activity of macro- and microorganisms. Bioremediation of hydrocarbon contaminated soils can be practised in situ or ex situ by either stimulating the indigenous microorganisms (biostimulation) or introducing adapted microorganisms which specifically degrade a contaminant (bioaugmentation). This investigation focused on ex situ remediation processes with special attention to the processes and microbiology of landfarming and thermal bioventing. Landfarming was investigated at pilot-scale and full-scale, and thermal bioventing at laboratory and pilot-scale. This study indicated that pilot-scale bioremediation by landfarming was capable of effecting a total petroleum hydrocarbon concentration (TPHC) reduction of 94% (m1m) from an initial concentration of 320 gkg-I soil to 18 gkg-I soil over a period of 10 weeks. Reactors receiving biosupplements showed greater rates of bioremediation than those receiving nutrients. Promotion of TPHC catabolism by addition of a commercial or a site-specific microbial biosupplement was similar. Seedling experiments proved that bioremediation did not necessarily leave the soil in an optimal condition for plant growth. The full-scale landfarming operation reduced the TPHC concentrations from 5 260 - 23 000 mgkg- I to 820 - 2335 mgkg- I soil over a period of 169 days. At full-scale, the larger fraction of more recalcitrant and weathered petroleums. and the less intensive treatment resulted in a slower rate of TPHC reduction than was found in the pilot-scale study. Three distinct decreases in the TPHC were observed during the full-scale treatment. These presented an ideal opportunity to investigate the microbiology of the soil undergoing treatment. The dominant culturable microorganisms were isolated and identified. The bioremediation process was dominated by Bacillus and Pseudomonas species. The method used to study the population was, however, biased to culturable, fast growing microorganisms which represent a small portion of the total microbial population. For this reason, a method to study the total eubacterial population in situ with rRNA targeted oligonucleotide probes was adapted and found to be a valuable technique. Soil microorganisms respiratory activity was investigated at different times in the full-scale treatment. A clear correlation between activity and degradation was recorded. The effect of a supplement. anaerobically digested sludge, was also assessed by this method. Thermal bioventing was investigated as an ex situ in-vessel treatment technology for small volumes of highly contaminated soils. This proved to be a viable technique for the bioremediation of petroleum hydrocarbons at laboratory-scale. Volatilisation contributed to at least 40% of the reduction. Of the two supplements evaluated. dried sludge promoted degradation to a greater extent than chicken manure. The pilot-scale study proved that a chemical contaminant reduction of at least 50% could be achieved in 13 weeks by thermal bioventing. Of the supplemented reactors. the presence of dried sludge and commercial biosupplement etfected the largest contaminant decrease. As a possible supplement to increase the rate of bioremediation. dried anaerobically digested sludge was more effective than chicken manure. A parallel laboratory-scale experiment gave similar results. Gravimetric analyses were found to be conservative indications of the remediation process. The results of this study shed some light on our. still. limited understanding of bioremediation. The gap between the technology in the laboratory and field was narrowed and a better understanding of the soil microbiology was achieved. Due to the limited control of environmental parameters in the case of landfarming. thermal bioventing was investigated and proved to be an effective alternative. The latter technology is novel in Southern Africa. / Thesis (Ph.D.)-University of Natal, Pietermaritzburg, 1996.

A final cover on a waste impoundment is the main physical barrier between the waste impoundment and the environment designed to protect against physical, chemical and biological factors isolating the waste from the atmospheric environment. Since the early 1990‟s regulators in the United States have started accepting vegetation covers in lieu of the prescriptive covers. Currently in South Africa, data that provide field performance comparisons of alternative vegetation covers are few or non-existent; hence a research program was undertaken by an industrial corporation in South Africa to determine the potential use of vegetation covers. In proposing a practical way forward, the Company (AECI Limited) reached an understanding with the Regulators that a vegetated evapotranspiration (ET) cover, would be acceptable provided that its performance in limiting surface water infiltration (and subsequent leaching) could be quantitatively demonstrated. The overall object of this research was to determine the capability of vegetation cover to limit effluent leaching from a waste impoundment. Analysis of the following sub-objectives were required to address and give answers to this study (1) determine, as accurately as possible a climatic water balance on the vegetation covers, (2) determine the geohydrological properties of the material of the waste impoundment, (3) determine the fate of the water i.e. proportion reused via evapotranspiration as opposed to the proportion infiltrating the waste body beneath the root zone and (4) determine the leaching potential below the waste. The study identifies and evaluates the climatic (above ground) and geohydrological (sub-surface) parameters used to estimate the water balance of the materials for a waste impoundment. The study then utilizes these parameters at the respective sites in a finite-element model, called the HYDRUS-2D model, to simulate the water balance of the material. The simulated water balance results were then compared against collected field data, which provide the evidence of the efficiency of a vegetation cover to limit effluent from the impoundment. / Thesis (M.Sc.)-University of KwaZulu-Natal, Pietermaritzburg, 2009.

[Truncated abstract] The synthetic hydrogel poly(2-hydroxyethyl methacrylate) (PHEMA) has been used as a biocompatible biomaterial in ocular devices, such as soft contact lenses, intraocular lenses and an artificial cornea. Due to its favourable properties as an already established (but non-biodegradable) biomaterial, PHEMA is an interesting candidate for use as a material for scaffolds in tissue engineering. A tenant of tissue engineering scaffolds is obtaining the appropriate porous morphology to allow for successful cellular attachment and support. PHEMA hydrogels exhibit varied morphological features, which range from non-porous (homogeneous) to macroporous (heterogeneous) and can be readily obtained by fine-tuning the polymerisation conditions. A desirable feature for matrices that are to be used as tissue supports is the ability to biodegrade in a biological environment. This thesis describes the preparation and enzymatic biodegradation behaviour of novel porous PHEMA hydrogels that have been crosslinked with biodegradable peptide-based crosslinking agents. Peptide-based crosslinking agents were designed to contain two terminal polymerisable groups flanking an internal biodegradable backbone. This backbone was specifically designed to be targeted by the proteolytic enzyme papain. The general design template allowed for the development of a synthetic methodology that was readily implemented for the production of a range of olefin-peptide conjugates. A suite of olefin-peptide conjugates of general structure I were synthesised, characterised and further tested with papain to determine their biodegradation properties. ... The second strategy for producing bioresorbable degradation fragments involved the incorporation of the highly hydrophilic comonomer, poly(ethylene glycol) PEG into the PHEMA backbone. The addition of PEG to PHEMA resulted in the formation of homogeneous hydrogels that had an improved hydrophilicity compared to their heterogeneous PHEMA counterparts. The synthetic conditions for the preparation of PHEMA and PHEMA-co-PEG hydrogels by photoinitiated polymerisation were thoroughly investigated. It was found that the pore morphology and general properties (non-porous to macroporous) of these hydrogels could be controlled by the appropriate choice of polymerisation conditions. The hydrogels were characterised by scanning electron microscopy, thermal gravimetric analysis and differential scanning calorimetry. The peptide-based crosslinking agents were successfully co-polymerised with the HEMA and PEGMA via photoinitiated polymerisation to provide a range of PHEMA and PHEMA-co-PEG hydrogels that displayed both homogeneous and heterogeneous hydrogel properties. The final crosslinked hydrogels were characterised by scanning electron microscopy and were subjected to enzymatic hydrolysis. The PHEMA-peptide conjugate hydrogels proved to be biodegradable, with degradation behaviour dependent on the hydrogel formulation and the length of the peptide-based crosslinking agent.

Orientadores: Lucia Helena Innocentini Mei, Nelson Eduardo Duran Caballero / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-13T07:57:38Z (GMT). No. of bitstreams: 1 Camargo_FranciscoAdaode_D.pdf: 5687735 bytes, checksum: 30f309fc3c8612bce1b126f965cd65a9 (MD5) Previous issue date: 2009 / Resumo: A produção de plásticos sintéticos tem aumentado ano após ano, por ser barato, resistente, etc. Mas, os especialistas advertem que o lucro obtido na industrialização e comercialização dos plásticos não pode por em risco o futuro da humanidade. Os fatos demonstram que o planeta já foi prejudicado, principalmente a fauna e a flora marinha. A solução para este problema é o desenvolvimento de materiais biodegradáveis, que garantam um desenvolvimento sustentável, onde o homem e o meio possam conviver sem causar prejuízos entre si. Com este princípio, buscamos neste trabalho o desenvolvimento de blendas biodegradáveis de polímeros naturais, com potencial para substituir alguns dos plásticos convencionais, contribuindo para o binômio produção versus preservação ambiental. A lignina é uma biomacromolécula, assim como o tanino, os quais são disponíveis em grande quantidade no Brasil. O outro componente da blenda, o copolímero de poli(3- hidroxibutirato-co-3-hidroxivalerato) ou PHBV, é uma biomolécula, termoplástico natural, biodegradável e biocompatível. Foi escolhida esta proporção (50:50)% (m/m), esta proporção foi a proporção estudada anteriormente, para a blenda de lignina de bagaço de cana com o PHBV, no aparelho Haake. Os estudos das propriedades mecânicas mostraram boas características de resistência, sendo processada na extrusora dupla rosca e injetada para a confecção dos corpos de prova. Foi estudada a biodegradação das amostras, em meio sólido, por ação dos fungos e bactérias do solo. As caracterizações das blendas (50:50) %, (m/m), ligninas, taninos, PHBV e PHB foram feitas por: Infravermelho com Transformada de Fourier (FT-IR), Calorimetria Diferencial de Varredura (DSC), Análise Dinâmico Mecânica (DMA), Microscopia Eletrônica de Varredura (MEV), Análise Elementar (CHN), Espectroscopia de Fluorescência, Fluorescência de Raios-X e Ressonância Magnética Nuclear de Hidrogênio (RMN- 1H). / Abstract: The production of synthetic plastics has been increasing year after year, for being cheap, resistant, and soon however, the specialists notice that the profit obtained in the industrialization and commercialization of the plastics should not put in risk the Humanity's future. The facts demonstrate that the planet was already harmed, mainly the fauna and the sea flora. The solution for this problem is the development of biodegradable materials to guarantee a sustained development, where the man and the environment have together without causing damages amongst themselves. With this objective, we decided to study in this work the development of biodegradable blends of natural polymer, with potential to substitute some of the conventional plastics, contributing thus the binomial production versus environmental preservation. The lignin is a biomacromolecule, as well as the tannin, theses components are available in great amount in the tropical countries like Brazil. The other component of the blends, the copolymer of poly(3-hydroxybutirate-co-3-hydroxyvalerate) or PHBV, is a natural biomolecule, thermoplastic, biodegradable and biocompatible. It was chosen this proportion (50:50) % (w/w), also this proportion was studied previously in our research group, for the blend of lignin of sugar cane bagasse with PHBV, in the apparatus Haake. The studies of mechanical properties because showed good resistance characteristics. The blends were processed in the twin screw extruders and injected for the making of the test sample. It was studied the biodegradation of the samples, in solid medium, in presence of the fungi and bacteria of the soil. The characterization of blends (50:50%) (w/w), lignins, tannins, PHBV's and PHB's were made by: Fourier Transform Infrared (FT-IR), Differential Scanning Calorimetry (DSC), Dynamic Mechanical Analysis (DMA), Scanning Microscopy Electronic (SEM), Elementary Analysis (CHN), Spectroscopy of Fluorescence, Fluorescence of ray-X and Nuclear Magnetic Resonance of Hydrogen (NMR -1H). / Doutorado / Ciencia e Tecnologia de Materiais / Doutor em Engenharia Química

Orientadores: Lucia Helena Innocentini Mei, Elke Jurandy Bran Nogueira Cardoso / Tese (doutorado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-15T18:48:38Z (GMT). No. of bitstreams: 1 Mariani_PilarDrummondSampaioCorrea_D.pdf: 18147924 bytes, checksum: 325f49ef8840be70ed59254449097128 (MD5) Previous issue date: 2010 / Resumo: O desenvolvimento de polímeros biodegradáveis tem como objetivo contribuir com a redução do volume de lixo plástico descartado no meio ambiente. Em vista disso, a utilização de polímeros naturais na confecção de blendas tem proporcionado o aproveitamento de recursos de fontes renováveis como e o caso do amido e da soja. Nesse trabalho, dando continuidade as pesquisas realizadas anteriormente no grupo de materiais biodegradáveis da Profa. Lucia H. Innocentini-Mei (FEQ/UNICAMP),foram utilizadas blendas a base de poli (e-caprolactona), amido de milho modificado, proteína isolada de soja (PIS) e sorbitol. As blendas foram preparadas através de extrusão em extrusora mono-rosca e prensagem a quente e as amostras assim obtidas foram submetidas a caracterização e estudo da biodegradação em diferentes solos, com o apoio do Laboratório de Microbiologia do solo da ESALQ/USP, sob a supervisão da Profa. Elke J.B. Cardoso. A caracterização dos materiais obtidos deu enfoque as propriedades térmicas, mecânicas, morfológicas e capacidade de biodegradação em solos de diferentes texturas, e com ou sem a adição de N-fertilizante. Observou-se que a incorporação de amido modificado e proteína isolada de soja foram responsáveis pela redução das propriedades térmicas e mecânicas dos materiais, mas, para muitas aplicações estas propriedades não são requisitos indispensáveis. Com relação à proteína isolada de soja, esta proporcionou a redução da relação carbono/nitrogênio (C/N) da blenda como esperado, atributo que foi decisivo durante o processo de biodegradacao das formulacoes em diferentes solos. A mineralizacao das formulações foi maior em solo de textura arenosa, com maior conversão de carbono a dióxido de carbono (CO2); por outro lado, o solo de textura argilosa não apresentou taxas altas de conversão de carbono a dióxido de carbono para as blendas, mas foi mais eficiente na formação de biomassa microbiana, comparado ao solo arenoso. / Abstract: The development of biodegradable polymers came to reduce the volume of plastic waste discarded in the environment. As a result, the use of natural polymers in the manufacture of blends has provided the use of renewable resources such as starch and soy. In this work, continuing the research done previously in the biodegradable materials group of School of Chemical Engineering School at State University of Campinas/ Brazil, supervised by Prof. Lucia H. Innocentini-Mei, blends of poly (e-caprolactone)/modified starch, soy protein isolate (SPI) and sorbitol were prepared by extrusion in single-screw extruder and hot pressing machine. The samples obtained were subjected to characterization and study of biodegradation in different soils, with the support of the Laboratory of Soil Microbiology (ESALQ/USP), under the supervision of Professor Elke J. B. N. Cardoso. The characterization of the material has focused on thermal, mechanical and morphological properties, and also on the biodegradation capacity in soils of different textures, and with or without the addition of N-fertilizer. It was observed that the incorporation of modified starch and soy protein isolate were responsible for the reduction of thermal and mechanical properties of materials but, for many applications, these properties are not necessaries. With respect to soy protein isolate (SPI), it reduced the carbon / nitrogen (C/N) of the blend as expected, an attribute which was decisive in the process of biodegradation of the studied formulations in different soils. Mineralization of the formulations was higher in sandy soil, with the higher conversion of carbon to carbon dioxide (CO2) compared to the clay soil, which did not show high rates of conversion but was more efficient in the formation of microbial biomass. / Doutorado / Ciencia e Tecnologia de Materiais / Doutor em Engenharia Química

Orientadores: Lucia Helena Innocentini Mei, Elisa Esposito / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia Quimica / Made available in DSpace on 2018-08-04T07:23:57Z (GMT). No. of bitstreams: 1 Mariani_PilarDrummondSampaioCorrea_M.pdf: 4205251 bytes, checksum: 489736fab0d98a4f88502814456a5e50 (MD5) Previous issue date: 2005 / Resumo: A consciência ambiental crescente, somada às políticas de gerenciamento de resíduos sólidos, tem impulsionado o desenvolvimento de materiais biodegradáveis par a substituição parcial dos plásticos de origem petroquímica em algumas áreas estratégicas como a de embalagens. No presente trabalho, avaliou-se a biodegrabilidade da blenda de PCL/Amido adipatado em solo, se acordo com a norma ASTM D5988-96 e Anderson et al. (1982); e em meio liquido de acordo com a norma ASTM 6691-01e Mergaert et al. (2000). No teste realizado em solo, a biodegradação foi acompanhada pela determinação da porcentagem de mineralização, através da medida da produção do dióxido de carbono e da perda de massa. O acompanhamento das alterações na cristalinidade da blenda foi feito um ambos os testes através de Calorimetria Exploratória Diferencial (DSC). Foi verificado que a blenda atingiu 70% de mineralização após 90 dias de incubação no solo. De acordo com a norma ASTM D 6400, esse valor permite concluir que a blenda é biodegradável. Por sua vez, a perda de massa da blenda incubada no solo foi maior do que no meio liquido, mostrando que a biodegradação no solo é bastante eficiente / Abstract: Increasing environmental concens and the waste management policies in the last decade have prompted the use of natural-based biodegradable materials instead od nonbiodegradable petrochemical - basead plastic. The present work it investigated the biodegradation in soil of a PCL/Starch-adipate blend, a natural ¿ based material, according to the ASTM D5988-96 standart and Anderson (1982). Furthermore, it was investigated the biodegradation of this material in liquid medium, according to the ASTM 6691-01 standart and Megaert et al (2000). During the soil tests,the biodegradation was indicated by 'CO IND. 2¿ evolution and mass loss measurements. In the liquid medium, the biodegradation was indicated by mass loss measurements only. Differential Scanning Calorimetry (DSC) was used to follow the crystallinity change in samples treated in liquid and solid medium. It wa observed that the blend reached 70% of mineralization after 90 days of soil incubation. According to the ASTM D 6400, this is a strong indication that the blend is biodegradable. The mass loss of blend sample incubated in soil was higher than for the sample incubated in liquid, showing that the biodegradation in soil was very efficient / Mestrado / Ciencia e Tecnologia de Materiais / Mestre em Engenharia Química