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The overall goal of this work was to investigate microbial activity leading to the anaerobic degradation of polycyclic aromatic hydrocarbons and an organophilic clay sediment cap used at a creosote-contaminated Superfund site. To determine whether or not PAHs were being degraded under anaerobic conditions in situ, groundwater and sediment porewater samples were analyzed for metabolic biomarkers, or metabolites, formed in the anaerobic degradation of naphthalene (a low-molecular weight PAH). In addition, a groundwater push-pull method was developed to evaluate whether the transformation of deuterated naphthalene to a deuterated metabolite could be monitored in situ and if conservative rates of transformation can be defined using this method. Metabolites of anaerobic naphthalene degradation were detected in all samples that also contained significant levels of naphthalene. Anaerobic degradation of naphthalene appears to be widespread in the upland contaminated aquifer, as well as within the adjacent river sediments. A zero-order rate of transformation of naphthalene-D₈ to naphthoic acid-D₇was calculated as 31 nM·d-¹. This study is the first reported use of deuterated naphthalene to provide both conclusive evidence of the in situ production of breakdown metabolites and an in situ rate of transformation. Methane ebullition was observed in areas of the sediment cap footprint associated with organophilic clay that was used a reactive capping material to sequester mobile non-aqueous phase liquid (NAPL) at the site. Anaerobic slurry incubations were constructed using sediment core samples to quantify the contribution of the native sediment and the different layers of capping material (sand and organophilic clay) to the overall methane production. Substrate addition experiments using fresh, unused organophilic clay, as well as measured changes in total carbon in organophilic clay over time supported the hypothesis that microbes can use organophilic clay as a carbon source. Quantitative PCR (qPCR) directed at the mcrA gene enumerated methanogens in field samples and incubations of native sediment and capping materials. Denaturing gradient gel electrophoresis (DGGE) was also performed on DNA extracted from these samples to identify some of the predominant microorganisms within the sediment cap footprint. The organophilic clay incubations produced up to 1500 times more methane than the native sediment and sand cap incubations. The organophilic clay field sample contained the greatest number of methanogens and the native sediment contained the least. However, the native sediment incubations had greater numbers of methanogens compared to their respective field sample and comparable numbers to the organophilic clay incubation. An increase in methane production was observed with the addition of fresh, unused organophilic clay to the already active organophilic clay incubations indicating that organophilic clay stimulates methanogenesis. In addition, organophilic clay retrieved from the field lost about 10% of its total carbon over a 300-day incubation period suggesting that some component of organophilic clay may be converted to methane. DGGE results revealed that some of the predominant groups within the native sediment and sediment cap were Bacteriodetes, Firmicutes, Chloroflexi, and Deltaproteobacteria. An organism 98% similar to Syntrophus sp. was identified in the organophilic clay suggesting this organism may be working in concert with methanogens to convert the organic component of organophilic clay ultimately to methane. The capacity of organophilic clay to sequester organic contaminants will likely change over time as the organic component is removed from the clay. This, in turn, affects the use of this material as a long-term remedial strategy in reduced, contaminated environments.

In 1997, a phytoremediation program began at a creosote-contaminated former railroad tie yard in Oneida, Tennessee with the planting of over 1000 hybrid poplar trees onsite. Creosote, a mixture of hazardous chemicals composed of 85% polycyclic aromatic hydrocarbons (PAH) had entered the site soil and ground water. After planting, a seasonal ground water testing program began that monitored the progress of remediation by measuring the concentration of the 10 predominant PAHs in the contaminant plume: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, chrysene, and benzo(b)fluoranthene. The concentrations of these compounds steadily decreased over time, but the role the trees played in the remediation was unclear. In order to gain a clearer understanding of the role the trees played in contaminant remediation, chemical analysis of tree tissue began. It was not known whether the trees were taking up PAH contaminants or their metabolites or if the rhizosphere zone created by the trees simply enhanced the ability of the site microflora to degrade the PAH. The objectives of this research were to (1) develop a suitable method for the chemical analysis of tree tissue collected from a field site, (2) determine if there were any chemicals not usually found in poplar trees that occurred in the trees growing over contamination, (3) determine if bud, bark, and twig tissue differed in their ability to predict ground water contamination, and (4) determine if a spatial correlation existed between the aromatic compounds in the tree tissue and the ground water total PAH plume. Two types of tree tissue/ground water comparisons were performed: spatial distribution of isoeugenol concentration in tree tissue with spatial distribution of total PAH in ground water over the area of interest; and the spatial distribution of the quantity of aromatic compounds in tree tissue with the spatial distribution of total PAH concentration in ground water. Due to unit discrepancies between the quantities of interest, all comparisons were made on a percentile basis. Initial tree sampling revealed that several compounds not usually present in poplar trees occurred only in those trees growing over contamination. In the first part of this study, the concentration of one of these chemicals, the substituted phenol isoeugenol, was compared with the concentration of total PAH in ground water from samples collected from February-March 2002. The bark tissue percentiles fell within 20 percentiles of ground water total PAH concentrations in 60% of the study area. The twig tissue showed slightly better agreement, with 67% of the study area differing from ground water by twenty percentiles or less. The second comparison took place over three sampling events: March 2001, July 2001, and February-March 2002. The number of unique aromatic compounds in bark, bud, and twig tissue was compared with the total PAH concentration in ground water. Twig tissue aromatic compound content was the most accurate predictor of ground water contamination among the tissue types. After excluding those chemicals likely to be interferences from consideration, twig tissue aromatic content agreed with ground water total PAH concentration to within 20 percentiles over 2/3 or more of the study area during each sampling event, suggesting the potential uptake of PAHs or their microbial metabolites as a mechanism of phytoremediation at the site. / Master of Science

Phytoremediation is an attractive remediation technology due to its relative low cost and maintenance requirement. Acceptance of phytoremediation requires that the contaminant removal mechanisms are characterized and demonstrated in the field. Quantification of contributions from each mechanism to the overall remediation rate is crucial for optimization of phytoremediation systems, risk management and prediction of the total remediation time. The objective of this research was to characterize and quantify removal mechanisms for naphthalene at a creosote-contaminated site with poplar trees in Oneida, Tennessee. Groundwater monitoring for seven years in the surficial aquifer at this site demonstrated a reduction in polycyclic aromatic hydrocarbons (PAHs) with selective removal of naphthalene and three-ring compounds. Naphthalene mass loss mechanisms investigated at this site are biodegradation in the saturated zone, volatilization and biodegradation in the vadose zone and phytovolatilization. This is probably the most comprehensive field study of PAH phytoremediation mechanisms conducted to date. The significance of this research is to contribute to predictions of remediation time and end result for phytoremediation of PAHs. The understanding of in situ factors controlling each mechanism can facilitate future optimization of phytoremediation systems as well as improve risk assessment and monitoring strategies. Biodegradation rates were determined for different conditions at this site with in situ respiration tests, laboratory soil microcosms and laboratory soil columns. The combined remediation mechanisms of volatilization and biodegradation in the vadose zone were investigated in the field and in laboratory columns. Field measurements show that lower groundwater elevations in the summer and early fall lead to elevated groundwater concentrations of naphthalene and increased volatilization. The increase in the fraction of the porespace occupied by gas (gas saturation) in the unsaturated zone during the summer and fall further enhances the volatilization by increasing effective diffusion rates. Water consumption and interception by the phytoremediation system are believed to enhance mass transfer to the vadose zone. Column experiments and field measurements show that more than 90% of the naphthalene vapors are biodegraded within 5-10 cm above the groundwater table. The data indicate that biodegradation increases the overall volatilization flux out of the source by 10-300 times, when the source is exposed directly to the gas phase. In situ the naphthalene is generally dissolved from the source into the groundwater and then volatilezed from the groundwater to the gas phase. Under these conditions biodegradation in the vadose zone will still indirectly have an enhancing effect on the flux out of the source. This is the result of removal naphthalene from the soil gas by biodegrdation driving removal from the groundwater by volatilization, which in turn drives dissolution form the source into the groundwater. Phytovolatilization was quantified in flux chambers mounted on trees and calculated from transpiration rates. A laboratory uptake study and analysis of tree cores from the site provided supplementary evidence for naphthalene uptake by poplar trees. Phytovolatilization was detected throughout the year and was highest in the summer and fall when the groundwater concentrations were highest and transpiration was active. The role of biodegradation relative to physical removal mechanisms was compared for a year, for winter and summer conditions and with and without the impact of phytoremediation. Biodegradation of naphthalene in the saturated zone dominates by orders of magnitude over the removal by volatilization and phytovolatilization of naphthalene at this site. The removal of the total residual naphthalene mass was estimated to require up to 100 years with phytoremediation, but more than twice as long without phytoremediation. The estimated removal of naphthalene was three times larger in the summer than in the winter due to slower biodegradation in the saturated zone and smaller rates of volatilization to the vadose zone in the winter. The research shows that phytoremediation enhances the overall naphthalene removal, mainly by stimulating faster biodegradation in the rhizosphere and promoting mass transfer of naphthalene to the vadose zone followed by rapid vadose zone biodegradation. In the future, phytoremediation research focusing on the capillary zone is desirable. / Ph. D.

Thesis (MScAgric)--Stellenbosch University, 2013. / ENGLISH ABSTRACT: The quality of wine is largely dependent on environmental conditions and recent studies have therefore focused on agricultural practices in terms of water, soil and biodiversity conservation. The industry aims to create sustainable practice and to protect the natural resources available. Sources of potential grape contamination include: vehicle pollution, pesticides, bushfires and wood preservatives used for trellising systems. The latter have come to the attention of the South African wine industry (e.g. creosote and Copper Chromium Arsenate (CCA) products) as they may have consequences for the environment and wine quality. Creosote is a known pollutant of soil and ground water and the volatile fraction has been monitored in air. Plants may also accumulate polycyclic aromatic hydrocarbons (PAHs), which constitute up to 85% of the mass of creosote, and of which some have been proven carcinogenic. Because of the health risks associated with it, creosote has therefore been restricted for use in most applications in Europe, and also in the United States, Canada and Australia. This study focussed on the sensorial and chemical analyses of environmental and wine samples taken from the area around the creosote stockyard to determine accumulation of creosote-derived compounds. Environmental samples were collected and analysed at different distances from the affected area, over two vintages. Wines were made from grapes grown in vineyard blocks adjacent to the stockyard, to determine the effect of distance and skin contact during alcoholic fermentation treatments on wine taint. A sensory panel was trained for descriptive analysis to determine the intensity of the taint. Analytical methods were developed for the analysis of volatile organic compounds (VOCs) by gas chromatography mass spectrometry (GC-MS) and polycyclic aromatic hydrocarbons by high performance liquid chromatography with diode array detection (HPLC-DAD). The sensory results obtained showed white and rosé wines were perceived as clean, whilst the red wines were associated with burnt rubber/tar taint. The perceived taint decreased as distance from the stockyard increased. Wines made from the Cabernet Sauvignon blocks adjacent to the stockyard also showed an increase of taint with the increase of skin contact. Chemical data obtained showed that the taint consisted of a complex mixture of compounds, each with its own pattern of retention within the vineyard and wine. Only m-cresol was found above odour threshold, and only in red wines. The synergistic effect of some compounds may lead to an increase in the perceived taint. Berries and leaves had higher concentrations of volatile compounds than wines. Leaf contamination varied and followed the general trend in literature where the plants with high lipid content and exposed leaf area were the most contaminated. There may be other compounds present in creosote emissions, aside from those investigated here, with sensory attributes related to the taint found in wines. These compounds are styrene, indene, benzene, toluene, isoquinoline and quinoline and should be included in further investigations. From the PAH analysis of environmental samples and wines, it is evident that the samples closest to the stockyard were affected the most. The contamination varied with the depth of the soil: some of the heavier compounds were found in the samples taken from the deeper levels, whilst nearly all other target compounds were present in the top layer of soil. The concentrations found in the environmental samples were lower than reported in literature. Wines had few PAHs present, but at much higher concentrations than is allowed by EU legislation. From this study it is evident that the stockyard had negative effects on the surrounding environment in terms of sensory and chemical contamination. Recommendations include area rehabilitation by means of bioremediation to protect resources and ensure sustainable and safe production of crops. Industrial emissions should also be regulated and restricted in agricultural areas. Furthermore the use of creosote should be revised, and prohibited for agricultural use. / AFRIKAANSE OPSOMMING: Die kwaliteit van wyn is grootliks afhanklik van die omgewingstoestande. Daarom fokus verskeie onlangse studies op landbou aktiwiteite en die invloed daarvan op die omgewing in terme van water, grond en biodiversiteit bewaring. The wyn industrie se doelwitte sluit volhoubare praktyke in, wat die natuurlike hulpbronne bewaar en beskerm. Druiwe kan deur middel van die volgende bronne besoedel word: brandstof uitlaatgasse, insekdoders, veldbrande, gifstowwe wat gebruik word vir houtperservering wat dan verder aangewend word vir opleistelsels. Houtperservering (Koper chroom arsenaat (CCA) en kreosoot) het veral in die laaste paar jaar onder aandag gekom in die wynbedryf van Suid-Afrika as gevolg van die invloed daarvan op die omgewing en die uiteindelike wynkwaliteit. Kreosoot is ‘n gekende gifstof wat verantwoordelik is vir grond en grondwater besoedeling en wat gemonitor word in die atmosfeer. Plante akkummuleer ook poli-sikliese aromatiese hidro-koolstowwe (PAHs), wat to 85% uitmaak van die massa van kreosoot. PAHs is karsinogenies en dus is daar baie navorsing op die molekules reeds gedoen. Die gesondheidsrisikos gepaardgaande met kreosoot het gelei tot die streng geregulasies tans ingestel in Europa, die Verenigde State, Kanada en Australië. Hierdie studie het gefokus op die sensoriese en chemiese analises van omgewings- en wyn-monsters geneem van die omliggende area van die kreosoot palewerf om die akkumulasie van kreosoot-afgeleide-verbindings. Omgewingsmonsters was versamel en geanaliseer om verskillende afstande vanaf die bron van besoedeling (palewerf) te ondersoek oor ‘n twee jaar periode. Wyne is gemaak van die druiwe wat afkomstig is van die blok aangeplant langs die palewerf. Die wyne is ondersoek in terme van afstand vanaf die kreosoot bron asook oenologiese invloede, dopkontak gedurende alkoholiese fermentasie, op die kontaminasie beskryf in wyn. Die wyne is ook oor ‘n twee jaar periode voorberei en sluit die 2011 en 2012 seisoen in. ‘n Sensoriese paneel is opgelei om die beskrywende analises op die wyn uit te voer met die doel om die intensiteit van kontaminasie te identifiseer. Analitiese metodes is ook ontwikkel vir die analise van vlugtige organiese verbindings(VOCs) met gas chromatografie-massa spektrometrie (GCMS) en poli-sikliese aromaties hidro-koolstowwe (PAHs) met hoë druk vloeistof chromatografie. Die sensoriese resultate bekom het wit en rosé wyne as skoon laat blyk, terwyl rooi wyne meer geassosieer was met die gebrande rubber/ teer afgeur beskrywing. Die waargeneemde afgeur het afgeneem soos wat die afstand vanaf die palewerf toegeneem het. Wyne gemaak van die Cabernet Sauvignon blokke langsaan die palewerf het ook ‘n toename in die afgeur gehad met ‘n toename in dopkontak. Chemiese data bekom beeld uit dat die afgeur uit ‘n komplekse mengsel van verbindings bestaan, elk met sy eie patroon van verspreiding en verbinding in die wingerd as ook in die wyn. Net m-kresol was gevind bo die reuk drumpel, dit het ook net in rooi wyne voorgekom. Die sinergistiese effek van die verbindings mag egter bydra tot die waargeneemde afgeur. Druiwekorrels en blare het hoër konsentrasies van die vlugtige verbindings gehad as wat gemeet is in die wyne. Blaar kontaminasie het ook baie gewissel en het ooreengestem met die algemene tendens wat in literatuur beskryf is, naamlik dat plante met ‘n hoër lipid inhoud en grootter blaar oppervlak die meeste gekontamineer word. Daar mag egter nog baie ander verbindings bydra tot die waargeneemde afgeur gevind in die wyn. Spesifieke verbindings wat wel ‘n rol kan speel in kontaminasie en wat voorkom in die vlugtige gedeelte van kreosoot is styreen, indeen, benzeen, tolueen, isoquinoleen die vlugtige verbindings van kreosoot. Die verbindings moet ingesluit word vir verdere studies wat gedoen word op die kreosoot geassosieerde afgeur. Die PAHs analise op die omgewingsmonsters en wyne het gelei tot die bevestiging dat die naasliggende omgewing die meeste geaffekteer is. Die kontaminasie wissel in terme van die diepte in die grond wat die gifstowwe voorkom: die swaarder molekulêre verbindings is tot in die dieper vlakke waargeneem terwyl al die gemete verbindings in die boonste lae teenwoordig was. Die vlakke wat waargeneem is in dié studie is egter laer as wat voorheen in literatuur gevind is in ‘n kreosoot geaffekteerde omgewing. Wyn het PAHs teenwoordig gehad, alhoewel slegs twee verbindings gemeet is, het dit in hoër vlakke voorgekom as wat sekere Europese regulasies as toelaatbaar spesifiseer. Vanaf die studie resultate blyk dit, dat die palewerf se negatiewe invloed op die omliggende omgewing beide meetbaar was in sensories en chemiese kontaminasie. Voorstelle sluit onder andere die rehabilitasie van die omliggende omgewing deur middel van bioremediasie in. Om sodoende die natuurlike hulpbronne in die area te bewaar asook om volhoubare en veilige verbouing van gewasse te verseker. Industriële besoedeling en afval moet ook gereguleer word en beperk word in landbou areas. Verder moet die gebruik van kreosoot heroorweeg word en strenger regulasies moet in plek gestel word om aan internastionale standaarde te voldoen. / Financial support from Winetech, Trip and UFS

Creosoto, do grego sóteon, significa conservar. À substância descoberta em 1832 denominada Kreosot, foi atribuida a propriedade de \"evitar a putrefação\", de possuir o princípio anti-séptico contido no alcatrão derivado da madeira. O creosoto usado como agente preservador da madeira de origem mineral ou vegetal, consiste em uma mistura de fenóis e derivados fenólicos obtida durante a destilação do alcatrão da hulha; oleosa, cor escura, odor penetrante, sabor ardente e cáustico. Exposta à adversas condições de temperatura e umidade relativa, a madeira está sujeita à decomposição devido a agentes mecânicos, químicos, físicos e biológicos : bactérias; fungos; insetos como coleópteros e térmitas; \"brocas marinhas\", como moluscos e crustáceos. Os fungos e insetos xilófagos são os principais responsáveis pelas maiores perdas em madeira. Considerado um dos mais eficientes preservadores da madeira, o creosoto é largamente utilizado em dormentes ferroviários, protegendo-os do ataque de certas espécies de fungos e térmitas ou cupins. Dormente é o elemento da superestrutura ferroviária que recebe e transmite, ao lastro, os esforços produzidos pelas cargas dos veículos; serve de suporte aos trilhos, permite sua fixação e mantém invariável a bitola. As ferrovias brasileiras têm cerca de 30.000 km de linhas férreas com 60 milhões de dormentes de madeira. A manutenção da malha toda demanda a troca de pelo menos 4 milhões de dormentes por ano. Esses dormentes em desuso são depositados ao longo das ferrovias ou empilhados em galpões com conseqüente desperdício de matéria-prima que se torna excelente abrigo para insetos roedores e animais peçonhentos, além de poder ser foco de incêndios. Na procura por produtos substitutivos do creosoto, foram encontrados dois produtos químicos, o Arsenato de cobre cromatado e o Borato de cobre cromatado; o primeiro tão ou mais tóxico que o creosoto e o segundo sem a mesma eficiência. Os materiais alternativos como aço e material plástico, ainda não competem com os de madeira, no entanto os de concreto sinalizam essa competitividade. A Estrada de Ferro Carajás da Companhia Vale do Rio Doce foi escolhida para estudo da situação atual de todos os dormentes da linha principal, com 892 km, para programar sua substituição. Devido a sua pequena extensão, foi verificada toda a malha ferroviária, ou seja, o universo da pesquisa. A investigação consistiu de : levantamento dos tipos de madeiras usadas como dormentes; condições de degradação; produtos químicos utilizados em seu tratamento; levantamento quantitativo dos dormentes a serem substituídos até 2010; tipo de dormentes utilizados; testemunho das atividades descritas através de fotografias. Esse levantamento permitiu elaborar a programação de troca dos dormentes da Estrada de Ferro Carajás. / Creosote, from the Greek, sóteon, means to conserve. To this substance, discovery in 1832 called kreosot, was meant to avoid the deterioration. The creosote used as a preservation of wood came from two different forms, mineral and from plants, and it is a mixture of different kinds of phenols. The Creosote is dark with a really strong smell. When the wood is exposed to a vast conditions of temperatures or even humidity, it can suffer four different kind of deterioration - chemical, mechanical, physical and the biological, such as bacteria, fungi; insects and others. The fungi and the insects cause the most problems in the wood. The creosote is one of the best preservers of the wood. It is used on crossties, protecting then from the fungi or even the termites. The crosstie is the element of Railways that transmit all the efforts from the vehicles for the ballast. The Brazilian railway have near 30.000 km, with 60 millions of wood crossties. To maintain all of those crossties is necessary at least, to change for news one, four millions of crossties each year. Those crossties are all over the railways or even inside buildings, that can even calls for insects, snakes, rats, or something like, even they can catch on fire. Searching for chemical products that can substitute the creosote, two products were found, such as CCA and CCB. However, the first one is very toxic (even more toxic than creosote), and the other doesn\'t have the same effect like the creosote for the fungi and termites. The alternatives crossties such as steel, concrete and plastic are not as good as the wood crossties, and can also have the same problem of disposal, like the concrete, for example. But now in Brasil, those kind of crossties are becoming more available specially with the new experiments that are taking place in Estrada de Ferro Carajás, however those experiments are recent, then they don´t have a result yet. This Railway was chosen to study the real situation of all wood crossties at all its extension, 892 km. On this research, all kinds of crossties in Estrada de Ferro Carajás were investigated, then the real conditions of those crossties, all the kinds of chemical products used on the preservation of the wood, and the study to find the number of crossties discarded until 2010 and the photographs of the crossties with problems. With all those activities, the Program of the replacement of the crossies at the Estrada de Ferro Carajás could be finished.

Uncertainty of predicted change in precipitation frequency and intensity motivates the scientific community to better understand, quantify, and model the possible outcome of dryland ecosystems. In pulse dependent ecosystems (i.e. monsoon driven) soil moisture is tightly linked to atmospheric processes. Here, I analyze three overarching questions; Q1) How does soil moisture presence or absence in a shallow or deep layer influence the surface energy budget and planetary boundary layer characteristics?, Q2) What is the role of vegetation on ecosystem albedo in the presence or absence of deep soil moisture?, Q3) Can we develop empirical relationships between soil moisture and the planetary boundary layer height to help evaluate the role of future precipitation changes in land surface atmosphere interactions?. To address these questions I use a conceptual framework based on the presence or absence of soil moisture in a shallow or deep layer. I define these layers by using root profiles and establish soil moisture thresholds for each layer using four years of observations from the Santa Rita Creosote Ameriflux site. Soil moisture drydown curves were used to establish the shallow layer threshold in the shallow layer, while NEE (Net Ecosystem Exchange of carbon dioxide) was used to define the deep soil moisture threshold. Four cases were generated using these thresholds: Case 1, dry shallow layer and dry deep layer; Case 2, wet shallow layer and dry deep layer; Case 3, wet shallow layer and wet deep layer, and Case 4 dry shallow and wet deep layer. Using this framework, I related data from the Ameriflux site SRC (Santa Rita Creosote) from 2008 to 2012 and from atmospheric soundings from the nearby Tucson Airport; conducted field campaigns during 2011 and 2012 to measure albedo from individual bare and canopy patches that were then evaluated in a grid to estimate the influence of deep moisture on albedo via vegetation cover change; and evaluated the potential of using a two-layer bucket model and empirical relationships to evaluate the link between deep soil moisture and the planetary boundary layer height under changing precipitation regime. My results indicate that (1) the presence or absence of water in two layers plays a role in surface energy dynamics, (2) soil moisture presence in the deep layer is linked with decreased ecosystem albedo and planetary boundary layer height, (3) deep moisture sustains vegetation greenness and decreases albedo, and (4) empirical relationships are useful in modeling planetary boundary layer height from dryland ecosystems. Based on these results we argue that deep soil moisture plays an important role in land surface-atmosphere interactions.

Creosoto, do grego sóteon, significa conservar. À substância descoberta em 1832 denominada Kreosot, foi atribuida a propriedade de \"evitar a putrefação\", de possuir o princípio anti-séptico contido no alcatrão derivado da madeira. O creosoto usado como agente preservador da madeira de origem mineral ou vegetal, consiste em uma mistura de fenóis e derivados fenólicos obtida durante a destilação do alcatrão da hulha; oleosa, cor escura, odor penetrante, sabor ardente e cáustico. Exposta à adversas condições de temperatura e umidade relativa, a madeira está sujeita à decomposição devido a agentes mecânicos, químicos, físicos e biológicos : bactérias; fungos; insetos como coleópteros e térmitas; \"brocas marinhas\", como moluscos e crustáceos. Os fungos e insetos xilófagos são os principais responsáveis pelas maiores perdas em madeira. Considerado um dos mais eficientes preservadores da madeira, o creosoto é largamente utilizado em dormentes ferroviários, protegendo-os do ataque de certas espécies de fungos e térmitas ou cupins. Dormente é o elemento da superestrutura ferroviária que recebe e transmite, ao lastro, os esforços produzidos pelas cargas dos veículos; serve de suporte aos trilhos, permite sua fixação e mantém invariável a bitola. As ferrovias brasileiras têm cerca de 30.000 km de linhas férreas com 60 milhões de dormentes de madeira. A manutenção da malha toda demanda a troca de pelo menos 4 milhões de dormentes por ano. Esses dormentes em desuso são depositados ao longo das ferrovias ou empilhados em galpões com conseqüente desperdício de matéria-prima que se torna excelente abrigo para insetos roedores e animais peçonhentos, além de poder ser foco de incêndios. Na procura por produtos substitutivos do creosoto, foram encontrados dois produtos químicos, o Arsenato de cobre cromatado e o Borato de cobre cromatado; o primeiro tão ou mais tóxico que o creosoto e o segundo sem a mesma eficiência. Os materiais alternativos como aço e material plástico, ainda não competem com os de madeira, no entanto os de concreto sinalizam essa competitividade. A Estrada de Ferro Carajás da Companhia Vale do Rio Doce foi escolhida para estudo da situação atual de todos os dormentes da linha principal, com 892 km, para programar sua substituição. Devido a sua pequena extensão, foi verificada toda a malha ferroviária, ou seja, o universo da pesquisa. A investigação consistiu de : levantamento dos tipos de madeiras usadas como dormentes; condições de degradação; produtos químicos utilizados em seu tratamento; levantamento quantitativo dos dormentes a serem substituídos até 2010; tipo de dormentes utilizados; testemunho das atividades descritas através de fotografias. Esse levantamento permitiu elaborar a programação de troca dos dormentes da Estrada de Ferro Carajás. / Creosote, from the Greek, sóteon, means to conserve. To this substance, discovery in 1832 called kreosot, was meant to avoid the deterioration. The creosote used as a preservation of wood came from two different forms, mineral and from plants, and it is a mixture of different kinds of phenols. The Creosote is dark with a really strong smell. When the wood is exposed to a vast conditions of temperatures or even humidity, it can suffer four different kind of deterioration - chemical, mechanical, physical and the biological, such as bacteria, fungi; insects and others. The fungi and the insects cause the most problems in the wood. The creosote is one of the best preservers of the wood. It is used on crossties, protecting then from the fungi or even the termites. The crosstie is the element of Railways that transmit all the efforts from the vehicles for the ballast. The Brazilian railway have near 30.000 km, with 60 millions of wood crossties. To maintain all of those crossties is necessary at least, to change for news one, four millions of crossties each year. Those crossties are all over the railways or even inside buildings, that can even calls for insects, snakes, rats, or something like, even they can catch on fire. Searching for chemical products that can substitute the creosote, two products were found, such as CCA and CCB. However, the first one is very toxic (even more toxic than creosote), and the other doesn\'t have the same effect like the creosote for the fungi and termites. The alternatives crossties such as steel, concrete and plastic are not as good as the wood crossties, and can also have the same problem of disposal, like the concrete, for example. But now in Brasil, those kind of crossties are becoming more available specially with the new experiments that are taking place in Estrada de Ferro Carajás, however those experiments are recent, then they don´t have a result yet. This Railway was chosen to study the real situation of all wood crossties at all its extension, 892 km. On this research, all kinds of crossties in Estrada de Ferro Carajás were investigated, then the real conditions of those crossties, all the kinds of chemical products used on the preservation of the wood, and the study to find the number of crossties discarded until 2010 and the photographs of the crossties with problems. With all those activities, the Program of the replacement of the crossies at the Estrada de Ferro Carajás could be finished.

Human activities are changing wildfire regimes globally through ignition, spread of invasive species, fire suppression, and climate change. Because of this, ecosystems are experiencing novel fire regimes that may alter plant growth and patterns of succession. Annual growth rings are one metric that can track changes in tree and shrub growth patterns over time in response to changing fire frequency. In Chapter 1 we explored the effects of fire on resprouting native shrubs in the Mojave Desert. Fires are becoming increasingly frequent due to the spread of highly flammable invasive grasses in the region. We monitored growth and fruit production of Larrea tridentata D.C. (creosote bush) on burned and unburned transects from three independent 2005 wildfires. Even though creosote has a high fire mortality rate, we found that resprouting creosote produced 4.7 times the amount of fruit and had stems that grew nearly twice as fast compared to creosote in unburned areas. Our data suggest that creosote can resprout after fire and thrives in its growth rates and reproduction in post-fire environments. In Chapter 2 we used annual Basal Area Increment to investigate how fire suppression has altered facilitation and competition interactions through stages of succession in mixed aspen-conifer forests. We found that aspen had lower growth rates in mixed aspen-conifer stands compared to aspen dominant stands. We also found that aspen growing with an associated fir tree due to facilitation had increasingly lower growth rates over time than those growing independently. Fir trees in mixed stands were facilitated over time by associated aspen trees while fir trees growing in association and independently in aspen stands showed no statistical difference from each other but grew better than independent fir trees in mixed stands. Our data suggest that restoring a more frequent fire regime will balance competitive interactions between aspen and conifer in subalpine forests.

The rising use of natural products creates an imperative need for an enhanced awareness of the safety of current and new products making their way into the marketplace. An important example is natural products containing lignans as the principal active component. Despite their structural similarity the lignan of creosote bush can cause hepato- and renal toxicity while the lignans of flaxseed have no reported serious toxicity. This dissertation aimed to investigate the oxidative metabolism of such lignans to determine whether reversible, competitive interactions and/or bioactivation may explain the differences in their apparent toxicity.<p> The first objective was to study the metabolism and bioactivation of nordihydroguaiaretic acid (creosote bush) and secoisolariciresinol (flaxseed). Nordihydroguaiaretic acid metabolism in rat liver microsomes led to the production of three glutathione adducts formed via ortho¬-quinone reactive intermediates. This metabolism was independent of NADPH and thus attributed to autoxidation. Secoisolariciresinol metabolism yielded lariciresinol and no glutathione adducts suggesting an absence of bioactivation to reactive quinone intermediates.<p> The second objective was to study the autoxidation of nordihydroguaiaretic acid. The major autoxidation product was a unique, stable schisandrin-like cyclolignan which was the result of nordihydroguaiaretic acid cyclization. The half-life of nordihydroguaiaretic acid in aqueous solution, pH 7.4, 37ºC is 3.14 hours suggesting the cyclolignan may be responsible for some of the biological effects of nordihydroguaiaretic acid.<p> The third objective was to study the inhibition of cytochrome P450 isoforms 1A2, 2B, 2C11 and 3A by lignans derived from creosote bush and flaxseed. None of the lignans caused irreversible inhibition. Both creosote bush and flaxseed lignans caused reversible inhibition of P450 enzyme activity that involved competitive or mixed-type inhibition, however the inhibition was present at nonphysiologically relevant concentrations. Activation of cytochrome P450 isoforms was also observed at low lignan concentrations. The results suggest that P450-mediated bioactivation or reversible inhibition cannot explain the differences in toxicity noted between the lignans of creosote bush and flaxseed.<p> This work suggests a minimal risk for drug-lignan interactions at P450 enzymes. Further studies are warranted to determine the presence and biological and toxicological role of the nordihydroguaiaretic acid cyclolignan in herbal preparations.