Nearly 250,000 sites with past and present potentially polluting activities need urgent remediation within Europe. Major pollutants include organochlorines (OCls), e.g. chlorinated ethenes (CEs) and hexachlorocyclohexanes (HCHs), mainly used as industrial solvents and pesticides, respectively. Due to improper handling and disposal, OCls contaminants are present in the soil or groundwater surrounding sites, where they have been produced or used. CEs and HCHs can undergo degradation by microorganisms indigenous to the soil or groundwater. Therefore natural attenuation (NA), relying on the in situ biodegradation of pollutants, is considered as a cost effective remediation strategy, yet it requires accurate monitoring methods. Compound specific isotope analysis (CSIA) is a powerful tool to provide information on the extent of degradation and, when combining two isotope systems (2D-CSIA), such as carbon (δ13C) and chlorine (δ37Cl), on reaction mechanisms. The diagnostic reaction-specific isotope enrichment factors (εC and εCl) were determined in laboratory experiments for the anaerobic degradation of PCE, TCE (Paper II) and α-HCH (Paper III) by mixed bacterial cultures enriched from CEs and HCHs contaminated sites, respectively. The related mechanism-specific εCl/εC ratios were calculated as 0.35 ± 0.11 (PCE), 0.37 ± 0.11 (TCE) and 0.52 ± 0.23 (α-HCH). These values are smaller than previously reported values for pure cultures. This is explained by the microbial community composition changes observed during degradation of PCE and α-HCH, which also reflect the variability of the microbial community at the field level. Furthermore, εCl/εC ratio might be bacteria specific. These values allowed the estimation of the extent of contaminant degradation at the respective study sites (Paper III and IV). Application of both isotope systems (δ13C and δ37Cl) led to comparable estimates. However the choice of representative ε values is crucial for an accurate assessment. These studies show that CSIA is useful to quantify in situ degradation of OCls contaminants and identify reaction pathways, by combining δ13C and δ37Cl. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.</p>

I investigated how land use and human activities affect the sources and cycling of carbon (C) in subtropical rivers. Annually rivers receive a large amount of terrestrial C, process a portion of this C and return it to the atmosphere as CO2. The rest is transported to the ocean. Land use and human activities can affect the sources and fate of terrestrial C in rivers. However, studies on these effects are limited, especially in the humid subtropics. I combined measurements of the partial pressure of dissolved CO2 (pCO2), C isotopes (13C and 14C) and solid-state 13C nuclear magnetic resonance (NMR) to study C cycling in three subtropical rivers in Texas, two small rivers (Buffalo Bayou and Spring Creek) and a midsized river (the Brazos). My pCO2 data show that small humid subtropical rivers are likely a large source of atmospheric CO2 in the global C cycle. My measurements on pCO2, C isotopic and chemical composition of dissolved inorganic C (DIC) and particulate organic C (POC) revealed four types of effects of land use and human activities on river C cycling. First, oyster shells and crushed carbonate minerals used in road construction are being dissolved and slowly drained into Buffalo Bayou and the lower Brazos and may be a source of river CO2 released to the atmosphere. Second, river damming and nutrient input from urban treated wastewater stimulate algal growth and reduce CO2 evasion of the middle Brazos. Third, urban treated wastewater discharge is adding old POC to the middle Brazos and decomposition of the old POC adds to the old riverine DIC pool. Fourth, agricultural activities coupled with high precipitation enhance loss of old organic C (OC) from deep soils to the lower Brazos, and decomposition of the old soil OC contributes to the old CO2 evaded. I document for the first time the river C cycling effects of the use of carbonate minerals in construction and the riverine discharge of urban wastewater. Results presented here indicate the need to study disturbed river systems to better constrain the global C budget.

Revised chronologies from Moroccan cave sites have raised questions concerning the timing of changes in human cultural behaviour in relation to past climate shifts. However, many of the inferences about past moisture regimes are based on external records. Therefore, this thesis aimed to develop a palaeoclimate record using oxygen and carbon isotope values (d18O and d13C) in Gerbillinae (gerbil) teeth from two Late Pleistocene cave sites, El Harhoura 2 and Taforalt, in Morocco. Since small mammals are not commonly used to construct proxy climate records, a modern isotope study was undertaken in northwestern Africa to understand the influences on the stable isotope composition of small mammal tissues in semi-arid and arid settings. The results from the modern study show that d18O composition of gerbil teeth is strongly correlated with mean annual precipitation (MAP), and therefore in arid settings reflects moisture availability. Predictably, the d13C values of the gerbil teeth reflected C3 and C4 dietary inputs, but arid and mesic sites could not be distinguished because of the high variability displayed in d13C. The d18O isotope-based MAP reconstructions suggest that the Mediterranean coastal region of North Africa did not experience hyper-arid conditions during the Late Pleistocene. The d13C values of the gerbil teeth show that C3 vegetation dominated in the Late Pleistocene, but there was a small amount C4 vegetation present at Taforalt. This indicates that small mammals are extremely sensitive to discreet shifts in past vegetation cover. Both the modern and archaeological studies demonstrated that the isotope values of molars and incisors differed. The results indicate that tooth choice is an important consideration for applications as proxy Quaternary records, but also highlights a new potential means to distinguish seasonal contexts. Comparisons of proxy climate records and cultural sequences at Taforalt and El Harhoura 2 show that Middle Stone Age occupations of both sites occurred during relatively humid and arid climate phases. The transition to the Later Stone Age appears to have taken place during a period of increased aridity, hinting that this cultural transition may be related to changing environmental conditions.

No description available.

abstract: Atmospheric particulate matter (PM) has a pronounced effect on our climate, and exposure to PM causes negative health outcomes and elevated mortality rates in urban populations. Reactions that occur in fog can form new secondary organic aerosol material from gas-phase species or primary organic aerosols. It is important to understand these reactions, as well as how organic material is scavenged and deposited, so that climate and health effects can be fully assessed. Stable carbon isotopes have been used widely in studying gas- and particle-phase atmospheric chemistry. However, the processing of organic matter by fog has not yet been studied, even though stable isotopes can be used to track all aspects of atmospheric processing, from particle formation, particle scavenging, reactions that form secondary organic aerosol material, and particle deposition. Here, carbon isotope analysis is used for the first time to assess the processing of carbonaceous particles by fog. This work first compares carbon isotope measurements (δ13C) of particulate matter and fog from locations across the globe to assess how different primary aerosol sources are reflected in the atmosphere. Three field campaigns are then discussed that highlight different aspects of PM formation, composition, and processing. In Tempe, AZ, seasonal and size-dependent differences in the δ13C of total carbon and n-alkanes in PM were studied. δ13C was influenced by seasonal trends, including inversion, transport, population density, and photochemical activity. Variations in δ13C among particle size fractions were caused by sources that generate particles in different size modes. An analysis of PM from urban and suburban sites in northeastern France shows how both fog and rain can cause measurable changes in the δ13C of PM. The δ13C of PM was consistent over time when no weather events occurred, but particles were isotopically depleted by up to 1.1‰ in the presence of fog due to preferential scavenging of larger isotopically enriched particles. Finally, the δ13C of the dissolved organic carbon in fog collected on the coast of Southern California is discussed. Here, temporal depletion of the δ13C of fog by up to 1.2‰ demonstrates its use in observing the scavenging and deposition of organic PM. / Dissertation/Thesis / Doctoral Dissertation Chemistry 2018

M.Sc. / Please refer to full text to view abstract

Le Crétacé a été une période d'instabilité climatique et du cycle du carbone, dont le CO2 atmosphérique a été désigné comme le driver majeur. Cependant, les reconstitutions du CO2 atmosphérique ne reflètent ni les dynamiques climatiques ni les grands évènements de perturbation du cycle du carbone décrits pour cette période. J'ai utilisé la composition isotopique de carbone de la plante fossile Frenelopsis (d13Cleaf) comme un nouvel proxy pour reconstituer le CO2 atmosphérique du Crétacé en termes de composition isotopique de carbone (d13CCO2) et de concentration (pCO2). La première courbe de d13CCO2 pour toute la durée du Crétacé a été construite à partir du d13C des carbonates marins. Sa comparaison avec des estimations de d13CCO2 à partir du d13Cleaf a révélé que les modèles développés jusqu'à maintenant ont une tendance à exagérer les valeurs de d13CCO2. Des estimations du fractionnement isotopique du carbone issu par des plantes (13Cleaf) obtenues à partir des nouvelles données d e d13Cleaf et d13CCO2 ont permis de reconstituer l'évolution à grande échelle de la pCO2. Ces résultats indiquent que le CO2 a probablement été une conséquence à long terme du changement climatique durant le Crétacé. Des cycles de d13CCO2 de ~1.2, ~2.1, ~5.4 et ~10.2 Ma ont été détectés, synchrones à ceux du niveau de la mer et à la cyclicité des paramètres de l'orbite terrestre décrits pour le Mésozoïque. Mes résultats fournissent une nouvelle perspective du système climatique et du cycle du carbone du Crétacé, dominés principalement par les paramètres orbitaux de la Terre et secondairement par des évènements catastrophiques de libération de CO2 d'origine volcanique dans l'atmosphère / The Cretaceous was a period characterized by strongly marked climate change and major carbon cycle instability. Atmospheric CO2 has repeatedly been pointed out as a major agent involved in these changing conditions during the period. However, long-term trends in CO2 described for the Cretaceous are not consistent with those of temperature and the large disturbance events of the carbon cycle described for the period. This raises a double question of whether descriptions of the long-term evolution of atmospheric CO2 made so far are accurate or, if so, atmospheric CO2 was actually a major driver of carbon cycle and climate dynamics as usually stated. In this thesis the close relationship between the carbon isotope composition of plants and atmospheric CO2 is used to address this question. Based on its ecological significance, distribution, morphological features and its excellent preservation, the fossil conifer genus Frenelopsis is proposed as a new plant proxy for climate reconstructions during the Cretaceous. The capacity of carbon isotope compositions of Frenelopsis leaves (d13Cleaf) to reconstruct past atmospheric CO2, with regards to both carbon isotope composition (d13CCO2) and concentration (pCO2), is tested based on materials coming from twelve Cretaceous episodes. To provide a framework to test the capacity of d13Cleaf to reconstruct d13CCO2 and allowing for climate estimates from carbon isotope discrimination by plants (?13Cleaf), a new d13CCO2 curve for the Cretaceous based on carbon isotope compositions of marine carbonates has been constructed. Comparison with d13Cleaf-based d13CCO2 estimates reveals that although d13CCO2 and d13Cleaf values follow consistent trends, models developed so far to estimate d13CCO2 from d13Cleaf tend to exaggerate d13CCO2 trends because of assuming a linear relationship between both values. However, given the hyperbolic relationship between ?13Cleaf and pCO2, by considering an independently-estimated correction factor for pCO2 for a given episode, d13Cleaf values may be a valuable proxy for d13CCO2 reconstructions. ?13Cleaf estimates obtained from d13CCO2 and d13Cleaf values were used to reconstruct the long-term evolution of pCO2. The magnitude of estimated pCO2 values is in accordance with that of the most recent and relevant model- and proxy-based pCO2 reconstructions. However, these new results evidence long-term drawdowns of pCO2 for Cretaceous time intervals in which temperature maxima have been described

Les plantations d’hévéa (Hevea brasiliensis) s’étendent vers des zones non traditionnelles de production en Thaïlande où des conditions plus sèches ont pu conduire à une diminution de la croissance des arbres et de la production de latex. Des paramètres physiologiques utiles pour sélectionner des génotypes adaptés sont nécessaires, comme l’efficience d’utilisation de l’eau (WUE). La discrimination isotopique du carbone est largement utilisée comme proxy pour WUE et peut être aisément utilisée dans des programmes de sélection pour la tolérance à la sécheresse. δ13C des feuilles et les échanges gazeux foliaires ont été mesurés sur de jeunes plants de dix clones d’hévéa cultivés en pot dans une pépinière. La gamme de δ13C des feuilles entre ces dix clones était restreinte et la corrélation entre δ13C et WUEi était significative que sous fort déficit de pression de vapeur saturante, ce qui signifie que la prédiction de WUE par δ13C serait peu précise. Il y avait une large gamme de δ13C entre les génotypes dans une collection de 49 génotypes sauvages d’hévéa cultivés dans le nord-est de la Thaïlande en saison sèche et en saison des pluies. δ13C était relativement stable avec une bonne corrélation entre les saisons. Cette étude montre que la variabilité génétique de δ13C est prometteuse pour des futurs programmes de sélections si une bonne corrélation entre δ13C et WUE peut être établie. L’absence de corrélation entre de δ13C du latex (δ13C-L) et des composés solubles extraits des feuilles (δ13C-S) prélevées sur des arbres saignés et non saignés âgés de 20 ans suggère que photosynthétats récemment produits se mélangent à un stock important d’hydrate de carbone impliqués dans la régénération du latex après la saignée. Donc, δ13C du latex n’est pas un indicateur pertinent de WUE / The rubber (Hevea brasiliensis) plantations extend to non-traditional area in Thailand where dryer conditions has been reported to impair the growth of rubber trees and latex production. Physiological parameters helpful for breeding adapted genotypes are required, such as water use efficiency (WUE). Carbon isotope discrimination is widely used as a proxy for WUE that can easily be used for selection and breeding programs for drought tolerance. Leaf δ13C and leaf gas exchange were measured on young saplings of 10 rubber clones growing in pot in a common garden. The range of leaf δ13C among 10 clones was narrow and the correlation between δ13C and WUEi was significant under high vapour pressure deficit only, which means the prediction of WUE by δ13C would have low precision. There were large δ13C variations among the genotypes at all seasons in a collection of 49 wild genotypes of rubber in Northeastern Thailand. δ13C was rather stable with a good correlation between rainy and dry season. The genetic variability of δ13C is promising for breeding if a good correlation between δ13C of leaf and WUE can be established. The lack of correlation between δ13C of latex (δ13C-L) and of leaf soluble compounds (δ13C-S) collected from tapped and untapped 20 year-old rubber trees suggests that recent photosynthates are mixed in the large pool of stored carbohydrates that are involved in latex regeneration after tapping. Thus δ13C of latex is not a relevant indicator of WUE of rubber trees

The global paleoclimate archive is lacking in tropical dendrochronology studies as a result of limitations from inconsistent tree-ring production imposed by precipitation-driven seasonality. The slash pine, Pinus elliottii Engelm. var. densa, is the dominant canopy species of Big Pine Key (BPK) rocklands and has been shown to produce complicated, but distinct, ring structures; however, traditional dendrochronology studies have not established correlations between ring width measurements and major climate drivers controlling South Florida precipitation. My study utilized the carbon (δ13C) and oxygen (δ18O) isotope records in the α-cellulose component of tree-rings to extract information about the physiological responses of trees to climate and tropical cyclone activity. The δ13C measurements in the earlywood and latewood of four P. elliottii var. densa trees were used to build a chronology (1922-2005) and to distinguish annual growth from intra-annual density fluctuations (IADFs). Empirical orthogonal functions were used to determine individual response to precipitation, El Niño-Southern Oscillation (ENSO), and the Atlantic Multidecadal Oscillation (AMO). There is a distinct relationship between the δ13C values of cellulose and ENSO; however the nature (direct vs. inversely correlated) is temporally controlled by the prevailing phase of the AMO. The appearance of some IADFs coincide with the timing of El Niño winters occurring during the cool AMO phase, resulting in enriched δ13C values. The additional precipitation may encourage tree growth, but subsequent dry periods may slow growth and cause the tree to employ water-conservation strategies. Tree growth is influenced by the major climate drivers and the control they exert over the timing of precipitation; however, growth is ultimately controlled by the microenvironment surrounding individual trees. The δ18O and δ13C values of the latewood cellulose were compared to tropical cyclone activity occurring within a 100km radius of BPK. Tropical storms and depressions appeared as anomalously depleted values in the δ18O residual record, reflecting large amounts of tropical rain. The effects of hurricanes varied by storm; however, many of the major hurricanes (category 3-5) were preserved as an enrichments in the δ13C value of the following earlywood season. The application of stable isotope analyses greatly increases the breadth of paleoclimate information available from the trees.

The carbon-isotope and palynological record through 580 m thick almost continuous brown coal in southeast Australia's Gippsland Basin is a relatively comprehensive southern hemisphere Middle Eocene to Middle Miocene record for terrestrial change. The carbon isotope δ13Ccoal values of these coals range from - 27.7‰ to - 23.2. This isotopic variability follows gymnosperm/angiosperm fluctuations, where higher ratios coincide with heavier δ13C values. There is also long-term variability in carbon isotopes through time. From the Eocene greenhouse world of high gymnosperm-heavier δ13Ccoal values, there is a progressive shift to lighter δ13Ccoal values that follows the earliest (Oi1?) glacial events around 33 Ma (Early Oligocene). The overlying Oligocene-Early Miocene brown coals have lower gymnosperm abundance, associated with increased %Nothofagus (angiosperm), and lightening of isotopes during Oligocene cooler conditions. The Miocene palynological and carbon-isotope record supports a continuation to the Oligocene trends until around the late Early Miocene (circa 19 Ma) when a warming commenced, followed by an even stronger isotope shift around 16 Ma that peaked in the Middle Miocene when higher gymnosperm abundance and heavier isotopes prevailed. The cycle between the two major warm peaks of Middle Eocene and Middle Miocene was circa 30 Ma long. This change corresponds to a fall in inferred pCO2 levels for the same period. The Gippsland data suggest a link between gymnosperm abundance, long-term plant δ13C composition, climatic change, and atmospheric pCO2. Climatic deterioration in the Late Miocene terminated peat accumulation in the Gippsland Basin and no further significant coals formed in southeast Australia. The poor correspondence between this terrestrial isotope data and the marine isotope record is explained by the dominant control on δ13C by the gymnosperm/angiosperm abundance, although in turn this poor correspondence may reflect palaeoclimate control. From the brown coal seam dating, the coal appears to have accumulated during a considerable part of the allocated 30 Ma Cenozoic time period. These brown coal carbon isotope and palynological data appear to record a more gradual atmospheric carbon isotope change compared to the marine record.