Irrigation using reclaimed wastewater can introduce organic contaminants and dissolved organic matter (DOM) to soils. Sorption of three common organic wastewater contaminants to five soils of diverse organic matter composition was studied both before and after the removal of soil carbohydrate and peptide components using acid hydrolysis. Results suggest that these polar components may block organic contaminants from accessing higher affinity sorption sites in soil organic matter. The sorptive fractionation of DOM by three mineral soils was studied to assess the terrestrial fate of this complex environmental matrix. Carboxyl- and aromatic-containing moieties appear to preferentially and reversibly sorb to mineral soils. Conversely, carbohydrate and peptide components of DOM preferentially remain in the aqueous phase while aliphatic moieties were selectively retained only by a soil with high surface area. This thesis illustrates that reclaimed wastewater should be applied to soils cautiously as it may degrade soil and groundwater quality.

Irrigation using reclaimed wastewater can introduce organic contaminants and dissolved organic matter (DOM) to soils. Sorption of three common organic wastewater contaminants to five soils of diverse organic matter composition was studied both before and after the removal of soil carbohydrate and peptide components using acid hydrolysis. Results suggest that these polar components may block organic contaminants from accessing higher affinity sorption sites in soil organic matter. The sorptive fractionation of DOM by three mineral soils was studied to assess the terrestrial fate of this complex environmental matrix. Carboxyl- and aromatic-containing moieties appear to preferentially and reversibly sorb to mineral soils. Conversely, carbohydrate and peptide components of DOM preferentially remain in the aqueous phase while aliphatic moieties were selectively retained only by a soil with high surface area. This thesis illustrates that reclaimed wastewater should be applied to soils cautiously as it may degrade soil and groundwater quality.

Our knowledge of how Arctic freshwater ecosystems will respond to continued climate change and variability is fundamentally limited by logistical difficulties of such remote research, resulting in relatively sparse long-term baseline data on these systems. This research applies a unique paired-watershed approach (i.e., two similar, adjacent lakes and catchments) to help address these limitations, which provided an opportunity to identify how broad-scale factors are filtered or modified by site-specific characteristics. My first main objective was to document the seasonal hydrochemical variability of runoff and influences on lake chemistry. Both lakes appear to be relatively insensitive to seasonal hydroclimatic variability, largely because periods of high discharge were also characterized by lower concentrations of dissolved and particulate matter, but also because of the relatively long lake water turnover time that suggests the effects of climatic and environmental changes would be felt later in these systems than in lakes and ponds with smaller lake volumes. My second objective was to investigate spatial and temporal trends in the lake diatom communities in order to refine subsequent paleoenvironmental reconstructions. A critical aspect of this objective was testing how faithfully the whole lake diatom community was represented in deep lake surface sediments where sediment cores are routinely collected. Most differences between the two lakes were largely accounted for with micro-environmental conditions associated with the specific sampling location. Also, both lakes exhibited a degree of disconnection between littoral benthic and profundal zones that manifested as an under-representation of the benthic community in deep lake surface sediments, with implications for paleoenvironmental interpretations. Finally, I present a multi-proxy record of environmental conditions in adjacent lakes spanning the period from pre-industrial times. Biogeochemical records reflected major changes in lake primary productivity and terrestrial organic matter accumulation beginning prior to 1950 in both lakes, pointing to profound environmental changes that culminated with the establishment of an appreciable diatom community in both lakes in the 1980s. Differences in the timing of changes between the two lakes point to differing threshold capacities to external forcings, and suggest that East Lake’s response to post-industrial climate change is advanced compared to West Lake. / Thesis (Ph.D, Geography) -- Queen's University, 2011-10-26 09:34:01.144

In April 2010, approximately 4.9 million barrels of oil were accidentally released into the Gulf of Mexico during the Deepwater Horizon Macondo Mc252 Oil Spill. Some of the surface oil was carried by prevailing winds and currents and reached the coast of Louisiana impacting marsh and marine ecosystems. One and a half years after this incident, a set of oiled marsh samples (2 grab samples) coupled with nearby subtidal and intertidal cores (12 cores) were collected from Barataria Bay, Louisiana to determine the probable source of petroleum residues present and to characterize the chemical composition of the oil. Plus, pre-spill core which was collected from Barataria Bay in 2007 was analyzed to identify the background hydrocarbon composition of the area. Polycyclic aromatic hydrocarbons (PAH), total petroleum hydrocarbons (TPH), biomarker, and stable carbon isotope compositions of selected samples were detected using a GC-MS and an elemental analyzer Conflo system coupled to a DeltaPlusXP isotope ratio mass spectrometer. The comprehensive chemical data allowed us to classify the pre and post-spill samples into 4 Groups. According to this classification, Group 1 and Group 2 samples had the highest concentrations of petroleum-derived hydrocarbons. Group 3 and background samples, on the other hand, was dominated by biogenic signatures. Although a direct connection between the detected and spilled Macondo oils results are complicated due to confounding factors (e.g., already present hydrocarbons and weathering processes), our biomarker data indicates that both oils have similar signatures. This close genetic relationship was also identified by stable carbon isotope analysis. The impact of the Macondo Mc252 Oil Spill in Barataria Bay appears to be limited to areas closer to the source. The oil has undergone moderate weathering and has penetrated into, the at least, the top 9 cm sediments. Additionally, to examine the decadal-scale history of sedimentation in these marshes, a sediment core was analyzed for the radioisotope 137Cs. The observed sedimentation rate of 0.39 cm/yr shows that oil pollutant input into Barataria Bay has been ongoing for at least 50-60 years.

Thesis (Ph. D.)--Earth and Atmospheric Sciences, Georgia Institute of Technology, 2006. / Michael Bergin, Committee Member ; E. Michael Perdue, Committee Chair ; Ching-Hua Huang, Committee Member ; Ellery Ingall, Committee Member ; Martial Taillefert, Committee Member. Vita. Includes bibliographical references.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esta dissertação tem por objetivo o estudo geoquímico detalhado em poço da Bacia do Paraná, mais especificamente na cidade de Herval (RS), visando preencher algumas das lacunas existentes em termos de geoquímica orgânica da Formação Irati. Com base nos dados de carbono orgânico total, enxofre total, resíduo insolúvel, raios-gama, isótopos de carbono da matéria orgânica, pirólise Rock-Eval e biomarcadores individualizaram-se dez unidades quimioestratigráficas. Biomarcadores foram usados na caracterização dos ambientes deposicionais, na discriminação da origem da matéria orgânica e da influência da litologia. O ambiente deposicional das unidades A, B, C é óxico com salinidade normal. O topo da unidade B representa a superfície de inundação máxima, onde os valores de COT aumentam. Com base nos biomarcadores caracterizou-se um paleoambiente deposicional com alguma tendência anóxica. Nas unidades D e G ocorrem os folhelhos intercalados com carbonatos. Nestas, a concentração de COT é acima de 1%, porém, somente na unidade G há bom potencial gerador para gás e condensado. As unidades E e I apresentam elevados teores de carbono orgânico total, chegando a 16%. Os dados de pirólise Rock-Eval indicam um bom a excelente potencial gerador para óleo e gás. Os dados isotópicos possibilitaram a divisão da Formação Irati, no poço em estudo, em três ciclos. O primeiro, da base para o topo, corresponde ao Membro Taquaral, os outros dois correspondem ao Membro Assistência. No Membro Assistência o δ13C varia de acordo com a salinidade, aumento da produtividade primária e da preservação da matéria orgânica (anoxia). / The current research had the main focus on the geochemical study of a borehole in the Parana Basin at Herval city (RS), aiming to fill some gaps in the organic geochemistry of the Irati Formation. Ten chemical-stratigraphic units were defined from analytical data of Total Organic Carbon (TOC), total sulfur, insoluble residue, gamma-rays, isotopes of organic carbon, Rock-Eval pyrolysis and biomarkers. Distributions the depositional environment, source of organic matter and the lithological influence were characterized by the relative abundance of biomarkers. The depositional environments of the units A, B, C were characterized as normal saline oxic. The top of unit B represents the maximum flooding surface with increased TOC values. Based on the biomarkers it was possible to characterize a depositional paleoenvironment with some anoxic tendency. Shales and carbonate intercalations occur in the units D and G. In these units, the TOC concentration is above 1%, but only in the G unit there is good potential to produce gas and condensate. The E and I units present high contents of total organic carbon close to 16%. The pyrolysis "Rock-Eval" data indicate a good to excellent potential for generating oil and gas. The isotopic data allowed division of the Irati Formation in three cycles. The first, from bottom to top, corresponds to the Taquaral Member, the other two cycles correspond to the Assistência Member. In the Assistência Member δ13C range varies according to salinity, primary productivity increases and the organic matter preservation (anoxic depositional environment).

Conselho Nacional de Desenvolvimento Científico e Tecnológico / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Esta dissertação tem por objetivo o estudo geoquímico detalhado em poço da Bacia do Paraná, mais especificamente na cidade de Herval (RS), visando preencher algumas das lacunas existentes em termos de geoquímica orgânica da Formação Irati. Com base nos dados de carbono orgânico total, enxofre total, resíduo insolúvel, raios-gama, isótopos de carbono da matéria orgânica, pirólise Rock-Eval e biomarcadores individualizaram-se dez unidades quimioestratigráficas. Biomarcadores foram usados na caracterização dos ambientes deposicionais, na discriminação da origem da matéria orgânica e da influência da litologia. O ambiente deposicional das unidades A, B, C é óxico com salinidade normal. O topo da unidade B representa a superfície de inundação máxima, onde os valores de COT aumentam. Com base nos biomarcadores caracterizou-se um paleoambiente deposicional com alguma tendência anóxica. Nas unidades D e G ocorrem os folhelhos intercalados com carbonatos. Nestas, a concentração de COT é acima de 1%, porém, somente na unidade G há bom potencial gerador para gás e condensado. As unidades E e I apresentam elevados teores de carbono orgânico total, chegando a 16%. Os dados de pirólise Rock-Eval indicam um bom a excelente potencial gerador para óleo e gás. Os dados isotópicos possibilitaram a divisão da Formação Irati, no poço em estudo, em três ciclos. O primeiro, da base para o topo, corresponde ao Membro Taquaral, os outros dois correspondem ao Membro Assistência. No Membro Assistência o δ13C varia de acordo com a salinidade, aumento da produtividade primária e da preservação da matéria orgânica (anoxia). / The current research had the main focus on the geochemical study of a borehole in the Parana Basin at Herval city (RS), aiming to fill some gaps in the organic geochemistry of the Irati Formation. Ten chemical-stratigraphic units were defined from analytical data of Total Organic Carbon (TOC), total sulfur, insoluble residue, gamma-rays, isotopes of organic carbon, Rock-Eval pyrolysis and biomarkers. Distributions the depositional environment, source of organic matter and the lithological influence were characterized by the relative abundance of biomarkers. The depositional environments of the units A, B, C were characterized as normal saline oxic. The top of unit B represents the maximum flooding surface with increased TOC values. Based on the biomarkers it was possible to characterize a depositional paleoenvironment with some anoxic tendency. Shales and carbonate intercalations occur in the units D and G. In these units, the TOC concentration is above 1%, but only in the G unit there is good potential to produce gas and condensate. The E and I units present high contents of total organic carbon close to 16%. The pyrolysis "Rock-Eval" data indicate a good to excellent potential for generating oil and gas. The isotopic data allowed division of the Irati Formation in three cycles. The first, from bottom to top, corresponds to the Taquaral Member, the other two cycles correspond to the Assistência Member. In the Assistência Member δ13C range varies according to salinity, primary productivity increases and the organic matter preservation (anoxic depositional environment).

Orientadores: Wanilson Luiz Silva, Wilson T. V. Machado / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Geociencias / Made available in DSpace on 2018-08-13T05:59:28Z (GMT). No. of bitstreams: 1 Goncalves_WinstonFernandodeLima_M.pdf: 1499014 bytes, checksum: 5c07da002115d9b89a6193825e176d9f (MD5) Previous issue date: 2009 / Resumo: Este trabalho apresenta concentrações sazonais de elementos maiores, menores e traço em testemunhos de sedimentos e águas intersticiais (água de poro) e de superfície do estuário do rio Morrão, situado na porção NE do sistema estuarino de Santos-Cubatão (Estado de São Paulo). Matéria orgânica na fase sólida e algumas espécies químicas como Cl-, F-, NH4+, NO2 -, NO3 -, PO4 3- e SO4 2- também são reportadas nas águas intersticiais e de superfície e discutidas em termos do ambiente físico-químico (pH, Eh e salinidade). O objetivo maior foi avaliar o risco de biodisponibilidade de metais e metalóides. A água foi amostrada por diálise in situ, usando coletores que realizam difusão, comumente chamados peepers. A região de estudo forma um complexo ambiente, onde indústrias (desde a década de 1950) coexistem com uma área do bioma Mata Atlântica e ecossistema de manguezal. Os sedimentos coletados no verão e inverno de 2007 foram silte-argilosos (lamosos), com elevadas concentrações de matéria orgânica (8,8 a 14,2%). As águas do verão (intersticial e superficial) exibiram maior salinidade e pH em relação às águas de inverno. Em contraste, os valores de potencial redox foram maiores no inverno, mostrando condições mais redutoras durante o verão. Concentrações de NO2 -, NO3 -, PO4 3- foram abaixo do limite de detecção instrumental após a diluição da amostra em 50X, enquanto Cl- e F- (este último com forte influência industrial) foram espécies que apresentaram maiores concentrações no inverno e verão, respectivamente. O conteúdo de SO4 2- foi maior nas águas de inverno (intersticial e superficial) em comparação com as águas de verão, sugerindo que sulfato redução deve ser o processo dominante pelo qual a matéria orgânica do sedimento é metabolizada durante a estação quente e úmida (mais redutora). Em adição, amônio apresentou maior concentração no verão, implicando no decréscimo dos níveis de Eh e condições mais alcalinas. Alumínio, Si, P e Fe foram fortemente concentrados nos sedimentos, mas mostraram baixas concentrações nas águas intersticiais e de superfície, devido às respectivas baixas solubilidades nas condições físico-químicas do estuário investigado. Variabilidade sazonal é indicada no presente estudo para alguns elementos (e.g. As, Ni e Zn), incluindo sedimentos e águas intersticiais e de superfície, como resultado das variações de Eh e pH do ambiente. Elevadas concentrações de sulfetos de ferro nos sedimentos parecem tamponar o sistema, promovendo a precipitação de sulfetos menos solúveis (diminuindo a concentração de As, Ni e Zn na água) / Abstract: This work presents the seasonal concentrations of major, minor and trace elements in sediment cores and interstitial (pore water) and overlying surface waters of the Morrão river estuary located in the northeast part of the Santos-Cubatão estuarine system, State of São Paulo, Southeast Brazil, in order to discuss the metal bioavailability. Organic matter content is shown in the solid phase, and some chemical species such as Cl-, F-, NH4+, NO2 -, NO3 -, PO4 3- and SO4 2- also are reported in interstitial and overlying waters. Geochemistry data are discussed in terms of the physico-chemical environment (pH, redox potential and salinity). Water was sampled by in-situ dialysis using diffusion-type pore water samplers, commonly called "peepers". The study region forms a vast environmental complex where industries (since 1950s) coexist with an area of Atlantic rain forest and mangrove systems. The sampled sediments in summer/2007 and winter/2007 were muddy, with organic matter content ranging between 8.8% and 14.2%. The summer waters (interstitial and overlying) exhibited higher salinity and pH values compared to winter waters. In contrast, redox potential values were higher in winter, showing more reducing conditions during summer. Concentrations of NO2 -, NO3 - and PO4 3- were below the instrumental limit of detection after a 1/50 dilution with deionized water, while Cl- and F- (the latter with strong industrial influence) were dominant species in winter and summer waters, respectively. The SO4 2- content was higher in winter waters (interstitial and overlying) in comparison with summer waters, suggesting that sulfate reduction must be the dominant process by which sediment organic matter is metabolized during the hot and humid season. In addition, ammonium concentrations were highest in summer, implicating in decrease of Eh levels and more alkaline conditions. Aluminum, Si, P, and Fe were strongly concentrated in sediments, but showed relative low values in both interstitial and overlying waters due to the respective low solubility in the physico-chemical conditions of the Morrão river estuary. Seasonal variability is indicate in the present study to some elements (e.g. As, Ni and Zn), including sediments and interstitial and overlying waters, as a result of the dominant Eh and pH conditions. High iron sulfide concentrations in the sediments seem to be a buffer, controlling the precipitation of less soluble sulfides. / Mestrado / Geologia e Recursos Naturais / Mestre em Geociências

Rapid warming in northern latitudes will lead to permafrost thaw and subsequent carbon remobilisa­tion and release to the atmosphere. To incorporate the permafrost carbon climate feedback in globalEarth System Models, it is of importance to know the carbon stored in the circum­Arctic permafrostregion as accurate and precise as possible. Whereas soil, Yedoma and delta carbon stocks are alreadyquantified, deep carbon stocks for vast areas of the current permafrost region are still unaccountedfor. The aim of this Master thesis project is to estimate the deep carbon stock (>3m) for Quaternarydeposits outside the known reservoirs. Therefore, 363 boreholes and exposures were compiled fromthe scientific literature. 244 sites provide profile descriptions (depositional environment, depth andthickness) and another 119 sites contain data to calculate carbon densities (ground ice content, coarsefraction (>1cm and/or >2mm), bulk density and total organic carbon). Data gaps were filled usinglocal, regional and global average facies values from the compiled dataset. For spatial upscaling,key regions are defined using the permafrost zone, overburden thickness and ice content. The fielddata compiled here shows disagreements with the Circum­Arctic Map of Permafrost and Ground­Iceconditions (Brown et al. 2002), which should be updated especially in thin and ice­poor regions. Atotal C stock of 1698 ±255 PgC is estimated for 3­25m in Quaternary deposits of the circum­Arcitcpermafrost region, next to the Yedoma domain (327 ­ 466 PgC, Strauss et al. 2017) and deltas (41 ­151 PgC, Hugelius et al. 2014). About 70% of the carbon is stored within 3­10m (1200 ±238 PgC).Due to a publication bias towards thick and organic­rich sediments in the literature, C stocks calcualtedhere might be overestimated. Additional to the Yedoma domain, 309 ±99 PgC are stored in ice­richdeposits of the continuous permafrost zone, a regions especially prone to thermokarst and deep carbonremobilisation. Thermokarst, thermo­fluvial erosion along rivers and coasts as well as carbon releasethrough inland water systems presents possible release mechanisms for stored carbon. The permafrostcarbon estimate determined here doubles the known carbon reservoir in the permafrost region and em­phasises the importance for possible deep carbon release with future permafrost thawing.

Ce travail aborde l’étude d’une sélection de structures de combustion provenant de Régismont-le-Haut (Hérault, France) et des Bossats (Seine-et-Marne, France) en suivant une méthode multiscalaire. Ces deux sites de plein air livrent une documentation archéologique riche permettant de renseigner pour le premier une phase récente de l’Aurignacien et une phase ancienne du Gravettien, entre autres, pour le second. Du point de vue méthodologique, la démarche retenue implique de débuter par l’analyse des données de terrain (échelle macroscopique), de poursuivre les investigations grâce à la micromorphologie (échelles méso- et microscopique) et finalement d’avoir recours à la géochimie organique (échelle moléculaire). Afin d’affiner les clefs de lecture des résultats archéologiques et de proposer de nouvelles pistes de réflexion, un programme d’expérimentation a également été conduit. La mise en œuvre conjointe de ces différentes approches complémentaires dans l’optique de croiser leurs résultats et leurs hypothèses interprétatives fait notamment la part belle à la prise en compte de la matière organique présente dans les sédiments des structures de combustion. Les résultats obtenus permettent à la fois de mieux cerner les modes de fonctionnement et d’utilisation des différentes structures tout en prenant en compte leur évolution taphonomique. Les questions des aménagements, de l’intensité du fonctionnement, des types de combustible et de la fonction sont abordées dans le cas des structures primaires, les foyers, mais les structures secondaires apportent également des informations en ce qui concerne les activités d’entretien. La mise en perspective de ces résultats acquis sur deux sites particulièrement bien préservés permet une discussion plus large de la place des structures de combustion au début du Paléolithique supérieur, période pour laquelle les pyrotechnologies demeurent un domaine encore trop méconnu des comportements humains. / This study treats a selection of combustion structures from Régismont-le-Haut (Hérault, France) and les Bossats (Seine-et-Marne, France) using a multiscalar approach. These two open-air sites provide an extremely rich archaeological documentation of, respectively, a recent phase of the Aurignacian and an early phase of the Gravettian (among others). Methodologically the study entails treating three scales of analysis, beginning with field data (macroscopic scale), followed by micromorphological investigation (meso- and microscopic scales), and finishing with geochemical analyses (molecular scale). An experimental program was also developed in order to refine our tools for interpreting our archaeological datasets, as well as to propose novel avenues of reflexion. The concomitant application of these complementary approaches and subsequent cross-examination of their respective results underlines the important role of organic matter in the combustion structure sediments. The results obtained allow for a better understanding of fire structure operation and use, as well as the taphonomic evolution. For primary structures questions regarded additional construction of the structures, intensity of use, types of fuel, and their function, while secondary structures brought to the table information regarding maintenance activities. The contextualization of results obtained from these two particularly well-preserved sites allows us to reflect more widely upon the role of combustion structures in the Early Upper Palaeolithic, a period during which pyrotechnology remains a little explored sphere of human behaviour.