Previous studies have shown significant warming through the 1990s in the West Antarctic Ice Sheet (WAIS); but the records used in those studies end in early 2000, preventing trend analysis into the latest decade. Fourteen new snowpits and firn cores were collected in 2010 and 2011, which have been combined with previous cores to extend the isotopic records over WAIS. Significance of these isotopic patterns across WAIS was determined and is used to re-evaluate the warming of the West Antarctic interior over recent decades. We find that isotopic records longer than 50 years are needed to assess climate trends due to decadal variability. When assessed over periods greater than 50 years, there is a statistically significant warming trend over central WAIS. However, the isotopes in the 2000s are anomalously low in the isotopic records, which challenge the recent suggestion that the warming trend is accelerating. We attribute the isotopic low over the most recent decade to the coupling effect of anomalously low temperatures over central WAIS and associated increase in sea ice in the adjacent seas. This work strongly indicates that decadal variability and likely climate trends are both driven, at least in part, by atmospheric variability in the tropics as well as at high latitudes.

Western Antarctica has been experiencing significant warming for at least the past fifty years. While higher Net Surface Mass Balance (SMB) over West Antarctica during this period of warming is expected, SMB reconstructions from ice cores reveal a more complex pattern during the period of warming. The mechanisms giving rise to SMB variability over the West Antarctic Ice Sheet (WAIS) are not well understood due to lack of instrumental data. The Southern Annular Mode (SAM) and El Niño Southern Oscillation (ENSO) are believed to contribute to WAIS SMB variability but the assumption has not been rigorously tested. SMB during years where SAM and ENSO are in extreme phases is compared to average SMB from the period 1979-2010. Additionally, atmospheric circulation anomalies are used to assess what circulation patterns accompany extreme modes of climate during the same period. The results suggest that significantly lower SMB occurs when SAM is in an extremely positive phase or ENSO is in an extremely negative phase. Additionally, atmospheric circulation anomalies show that certain circulation patterns accompany extreme modes of climate, which contribute to SMB variability over the WAIS. Ultimately, the location of low and high pressure cells is the best predictor for extreme accumulation events over the WAIS. These results are verified by assessing observed net SMB trends from a network of firn cores located from the central WAIS. Seven new firn cores are added to improve the spatial network of regional net SMB measurements. Reconstructed net SMB is calculated from new firn core records, and compared to the existing cores. The new suite of preliminary firn core records show the same significant decreasing trend that is observed in existing cores. This represents a negative region-wide SMB trend that is likely in part due to trends in SAM and ENSO.

No description available.

L’objectif principal de cette thèse était de comprendre la variabilité millénaire du CO2 atmosphérique durant le stade isotopique marin 6 (Marine Isotope Stage 6, MIS 6), l’avant dernière période glaciaire (185-135 ka BP). Durant la première partie de la période MIS 6 (185-160 ka BP), 6 oscillations climatiques millénaires peuvent être observées dans des indicateurs de la température antarctique, du phénomène de bascule bipolaire dans la région Atlantique Nord et de l’intensité des moussons des basses latitudes. Un cycle hydrologique intensifié et des vêlages d’iceberg dans l’Atlantique Nord pourraient avoir impacté la circulation atlantique méridionale de retournement (Atlantic Meridional Overturning Circulation, AMOC) durant MIS 6 (Margari et al., 2010). La reconstruction de CO2 atmosphérique à partir des carottes antarctiques peut fournir des informations clés sur le lien entre CO2 atmosphérique et variabilité climatique millénaire. Cependant, les enregistrements existants du CO2 à partir de la carotte de glace de Vostok ne montrent pas de variabilité millénaire du fait de trop mauvaises résolution et précision.Pour examiner comment le CO2 atmosphérique est lié avec le changement climatique sur les échelles de temps millénaires pendant le MIS 6, nous avons analysé 150 échantillons de CO2 atmosphérique obtenus à partir de la carotte EPICA Dome C (EDC) sur la période 189.4-135.4 ka BP. Une oscillation mineure et 5 oscillations majeures du CO2 atmosphérique pendant la première partie de la période du MIS 6 (189-160 ka BP) ont été découvertes. Cette variabilité est très liée avec la température antarctique. Pendant les périodes stadiales courtes dans l’Atlantique Nord, les variations de CO2 atmosphérique sont négligeables et découplées avec la variabilité de la température antarctique. Durant ces périodes, la force de l’upwelling dans l’océan austral pourrait ne par être suffisante pour impacter le CO2 atmosphérique. De plus, 2 modes de variations du CO2 sont présentes pendant la période du MIS 6. Le maximum de dioxyde de carbone 6 (carbon dioxide maxima 6, CDM 6) suit le réchauffement rapide de l’hémisphère Nord de seulement 100±360 ans, alors que les retards pour les CDM 3 et 4 sont bien plus longs, 1 100±280 ans en moyenne. Ces deux modes de variation du CO2 pourraient être liés à un changement de mode de l’AMOC de la première partie du MIS 6 au MIS 6.5. Ces deux phénomènes sont aussi observés pendant la dernière période glaciaire. Cependant, les données disponibles permettent seulement une discussion exploratoire des mécanismes responsables de la variabilité du CO2 pendant MIS 6. Comme les conditions aux limites de la dernière période glaciaire ne peuvent pas être appliquées au MIS 6, des données supplémentaires et des études par modélisation du MIS 6 sont nécessaires. / The main objective of this thesis is to understand the millennial variability of atmospheric CO2 during the Marine Isotope Stage 6 (MIS 6), the penultimate glacial, period (185─135 kyr BP). During the early MIS 6 period (185-160 kyr BP), 6 millennial-scale climate oscillations can be observed in proxy records of Antarctic temperature, the bipolar see-saw phenomenon in the North Atlantic region, and Monsoon intensity in low latitudes. An intensified hydrological cycle and iceberg calving in the North Atlantic may have impacted on the Atlantic Meridional Overturning Circulation during MIS 6 (Margari et al., 2010). Atmospheric CO2 reconstructions from Antarctic ice cores can provide key information on how atmospheric CO2 concentrations are linked to millennial-scale climate changes. However, existing CO2 records from the Vostok ice core do not show the millennial variability due to the lack of suitable temporal resolution and precision. To understand atmospheric CO2 variability during MIS 6, a precision of less than 2 ppm is mandatory, because there is a possibility that we could observe small CO2 variability of less than 5 ppm during the smaller Antarctic isotope maxima events as observed during the last glacial period (Ahn and Brook, 2014; Bereiter et al., 2012).To investigate how atmospheric CO2 is related with climate change on millennial time scales during MIS 6, we reconstructed 150 samples of atmospheric CO2 data from the EPICA Dome C (EDC) ice core during the MIS 6 period (189.4─135.4 kyr BP). One minor and five major variabilities of atmospheric CO2 during the early MIS 6 period (189─160 kyr BP) were found. These variabilities are highly matched with Antarctic temperature. During the short stadials in the North Atlantic, atmospheric CO2 variations are negligible and decoupled with temperature variations in Dome C. During this period, the strength of upwelling in the southern ocean might not be sufficient to impact on atmospheric CO2. In addition, 2 modes of CO2 variations are present in the MIS 6 period. Carbon dioxide maxima (CDM) 6 lags abrupt warming in the Northern Hemisphere by only 100±360 yrs, while the lags for CDM 3 and 4 are much longer, 1,100±280 yrs on average. Theses 2 modes of CO2 variations might be related with a mode change of AMOC from the earliest MIS 6 to MIS 6.5. These two phenomena also are observed during the last glacial period. However, the limited available proxy data permit only an exploratory discussion of the mechanisms responsible for CO2 variability during MIS6. Because the boundary conditions of the last glacial period cannot be applied to MIS 6, additional proxy data and multiple modelling studies conducted during MIS 6 period are needed.

Esta tese interpreta o registro ambiental de um testemunho de gelo antártico pela análise de elementostraço. Esse testemunho de gelo, daqui em diante chamado Mount Johns (MJ), foi coletado no manto de gelo da Antártica Ocidental (79°55’28”S e 94°23’18”W; 91,20 m de comprimento) no verão austral de 2008/09. O testemunho foi descontaminado e subamostrado no Climate Change Institute (University of Maine – Maine /EUA). As primeiras 2137 amostras, correspondentes aos 45 m superiores do testemunho, foram analisadas no espectrômetro de massas Element 2 do CCI para 24 elementos-traço (Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Li, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg e K). Essa parte do testemunho representa 125 anos (1883–2008) de registro, segundo datação relativa baseada na variação sazonal nas concentrações de Na, Sr e S e na identificação dos principais eventos vulcânicos ocorridos no período. A taxa de acumulação média no local de amostragem foi 0,21 m a-1 em eq. H2O no mesmo período de tempo. As concentrações são controladas pelas variações climáticas sazonais (verão/inverno), por mudanças na circulação atmosféricas, por anomalias de temperatura, pela distância de transporte e pelas fontes naturais e antrópicas desses aerossóis. Baseada na análise dos fatores de enriquecimento crustal e marinho e em correlações de Pearson, as concentrações de Al, Ba, Ca, Fe, K, Mg, Mn, Na, S, Sr e Ti são de origem natural. Poeira e solo de fontes continentais, oriundas principalmente de áreas áridas na Austrália, Nova Zelândia e Patagônia, são consideradas importantes fontes de Al, Mg e Ti. Aerossóis marinhos do Pacífico Sul, transportados para o continente antártico pelas massas de ar, são fontes predominantes de Na, Sr, K, S e Ca. Para os elementos Ba, Fe e Mn, tanto fontes crustais como marinhas são significativas. Adicionalmente, Mn e S apresentam um aporte considerável de origem vulcânica (variando de 20–30% na concentração total). Os resultados também mostram enriquecimento significativo nas concentrações de arsênio devido a atividades antrópicas. Foi observado concentrações médias da ordem de 1,92 pg g-1 antes de 1900, aumentando até 7,94 pg g-1 em 1950. Este enriquecimento está diretamente relacionado às emissões da mineração e fundição de metais não-ferrosos na América do Sul, principalmente no Chile. A queda na concentração de arsênio observado no século XXI (concentração média de 1,94 pg g-1 após 1999) é interpretada como uma consequência à introdução de leis ambientais (em 1994) para reduzir emissões desse elemento durante os processos de mineração e fundição de cobre no Chile. O modelo de trajetórias HYSPLIT mostra uma clara variação sazonal no transporte entre os meses de verão/outono e inverno/primavera, onde predomina o transporte de oeste durante o ano todo e um transporte secundário de nordeste durante o verão/outono. As correlações entre as concentrações médias dos elementos-traço estudados e o modelo de reanálises ERA-Interim para o período 1979–2008, indicam que as concentrações de aerossóis marinhos são fortemente influenciadas pelas condições meteorológicas, por exemplo, por anomalias na temperatura da superfície do mar e concentração de gelo marinho. / This thesis interprets the environmental record of an Antarctic ice core by the analysis of trace elements. This ice core, henceforward called Mount Johns (MJ), was collected in the West Antarctica ice sheet (79°55'28"S and 94°23'18"W; 91.20 m long) in the austral summer of 2008/09. The core was decontaminated and subsampled at the Climate Change Institute (CCI, University of Maine - Maine / USA). The first 2137 samples, corresponding to the upper 45 m of the core, were analyzed in the CCI's JRC Element 2 spectrometer for 24 trace elements (Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Li, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg and K). This part of the core represents a 125 years (1883– 2008) record, according to relative dating based on Na, Sr and S seasonal variations and on the identification of major volcanic events in the period. The mean accumulation rate for the sampling site was 0.21 m-1 in eq. H2O in the same time period. The concentrations are controlled by seasonal climatic changes (summer/winter), by changes in atmospheric circulation, temperature anomalies, the transport distance and the natural and anthropogenic sources of these aerosols. Based on analysis of crustal and marine enrichment factors and Pearson correlations, the Al, Ba, Ca, Fe, K, Mg, Mn, Na, S, Sr and Ti concentrations have natural origin. Dust and soil from continental sources, primarily coming from arid areas in Australia, New Zealand and Patagonia, are considered important sources of Al, Mg and Ti. South Pacific marine aerosols, transported to the Antarctic continent by air masses, are predominant sources of Na, Sr, K, S and Ca. For the elements Ba, Fe and Mn, both crustal and marine sources are significant. In addition, Mn and S show a considerable contribution of volcanic origin (ranging from 20-30% of the total concentration). The results also show significant enrichment in arsenic concentrations due to human activities. Before 1900 the mean concentration was approximately 1.92 pg g-1, rising to 7.94 pg g-1 in 1950. This enrichment is directly related to mining emissions and casting of non-ferrous metals in South America, mainly in Chile. The decrease in the arsenic concentration, observed in the twenty-first century (mean concentration of 1.94 pg g-1 after 1999) is interpreted as a consequence of the introduction of environmental laws (in 1994) to reduce emissions of this element during the cupper mining and smelting in Chile. The HYSPLIT trajectories model show a clear seasonal variation in transport between the summer/autumn all and winter/spring months, where predominates an eastward transport throughout the year and a secondary transport from the northeast during the summer/fall. Correlations between the mean concentrations of the studied trace elements and the ERA-Interim reanalysis models for the 1979-2008 period indicate that marine aerosols concentrations are heavily influenced by weather conditions, for example, by sea surface temperature and sea ice concentration anomalies.

Nous avons conçu, construit et testé un nouveau système pour la décontamination en ligne et l'analyse en continu de carottes de neige ou de glace des Alpes. L'eau de fusion obtenue à partir de la partie centrale des carottes est directement introduite dans un spectromètre de masse à quadrupole (ICP-QMS) et un conductimètre, pour la détermination en continu de différents éléments présents à l'état de traces et de la conductivité. Des échantillons sont également prélevés en discontinu pour la détermination de divers éléments présents à l'état de traces, des isotopes du Plomb et du Plutonium par spectrométrie de masse à secteur magnétique (ICP-SFMS) et par ICP-OES. L'eau de fusion obtenue à partir de la partie externe des carottes est quant à elle utilisée pour la détermination en semi-continu des Hydrocarbures Aromatiques Polycycliques (HAPs), avec extraction en ligne à l'aide de cartouches en phase solide.<br />D'importantes variations saisonnières des concentrations sont observées pour tous les éléments, aussi bien les éléments qui proviennent de manière prédominante de la croûte terrestre (Mg, Al) que les éléments enrichis par suite d'apports anthropiques (Pb). Pour comprendre ces variations à court terme, il est important de se référer aux rétro-trajectoires des masses d'air. D'autres paramètres importants sont la dynamique des inversions de températures et les caractéristiques de la couche limite. Ils jouent en effet un rôle majeur dans le transport et la dispersion des aérosols et des gaz à partir des sources d'émissions situées à basse altitude.<br />Les émissions les plus importantes de Plomb au cours de l'histoire ont eu lieu pendant les 19e et 20e siècles, et plus particulièrement des années 1950 aux années 1970. Pour déterminer si les variations observées dans la carotte du Colle Gnifetti reflètent fidèlement les variations des émissions dans les pays européens voisins, nous avons comparé les données obtenues pour la neige et la glace avec les données d'émission disponibles. De 1800 jusqu'à la première décennie du 20e siècle, les concentrations de Plomb ont augmenté de manière très marquée, atteignant un maximum dans les années 1920. Pendant les années 1920, les concentrations de Plomb décroissent rapidement d'un facteur deux, et restent à ce niveau pendant les deux décennies suivantes. Après la fin de la 2e guerre mondiale, les flux de retombées de Plomb augmentent de manière très importante par suite de l'utilisation des additifs au Plomb dans l'essence, et atteignent un maximum au milieu des années 1970. A partir de 1975, les concentrations de Plomb mesurées dans la neige et la glace du Colle Gnifetti commencent à décroître par suite des règlementations adoptées en Europe pour limiter les émissions de polluants.<br />Avant 1875, les concentrations de HAP étaient très basses: les concentrations observées dans la glace datant d'avant les années 1750 représentent très probablement le niveau de bruit de fond de ces composés. Les concentrations cumulées des HAP au cours de la décennie 1945-1955 sont supérieures d'un facteur dix aux valeurs de bruit de fond, alors que les concentrations cumulées de HAP* sont environ 40 à 50 fois plus élevées. A partir des années 1900, les concentrations de HAP augmentent de façon très importante, atteignant un maximum vers 1920. Pendant les années 1920, après la première guerre mondiale, la récession économique en Europe conduit à une chute des activités industrielles. A partir du milieu des années 1930, les concentrations de HAP doublent rapidement, atteignant un maximum pendant les années 1940. La concentration cumulée des HAP* les plus lourds décroit ensuite d'un facteur cinq de 1950 à 1975 alors que la concentration cumulée des HAP décroit d'un facteur deux. De 1975 à 2003, la concentration totale des HAP augmente à nouveau, approchant les valeurs des années 1910. De manière globale, les variations temporelles observées pour les HAP sont fortement corrélées aux variations des émissions anthropiques. Cependant, les variations détaillées sont difficiles à interpréter et pourraient être influencées par divers paramètres.<br />Le Plutonium est présent dans l'environnement par suite des essais nucléaires atmosphériques des années 1960, de la production des armes nucléaires et des rejets par l'industrie nucléaire au cours des 50 dernières années. Le profil de variations du Plutonium dans la neige et la glace du Colle Gnifetti met en évidence les trois périodes principales d'essais nucléaires atmosphériques.<br />Le rapport isotopique 206Pb/207Pb est compris entre 1.18 et 1.20 pour la glace datant d'avant 1700, en accord avec la composition des roches locale. Bien que les retombées de Plomb au Colle Gnifetti après les années 1900 soient presque entièrement dues à des apports anthropiques, on n'observe pas de variations importantes du rapport isotopique jusqu'en 1975. Ceci est lié au fait que la composition isotopique moyenne du Plomb dans l'essence et le pétrole utilisés était très semblable à la composition isotopique des roches et des sols locaux. Après 1975, on observe une décroissance brutale et forte du rapport isotopique 206Pb/207Pb, jusqu'à des valeurs proches de 1.11 en 1979-1980. Cette décroissance brutale est liée à une expérience réalisée entre 1975 et 1980 dans la région du Piémont au Nord-Ouest de l'Italie (Isotopic Lead Experiment).

Ice cores are considered the gold standard for recording past climate and biogeochemical changes. However, gas records derived from ice core analysis have until now been largely limited to centennial and longer timescales because sufficient temporal resolution and analytical precision have been lacking, except during rare times when atmospheric concentrations changed rapidly. In this thesis I used a newly developed methane measurement line to make high-resolution, high-precision measurements of methane during the late Holocene (2800 years BP to present). This new measurement line is capable of an analytical precision of < 3 ppb using ~120 g samples whereas the previous highest resolution measurements attained a precision of ± 4.1 ppb using 500-1500g samples [MacFarling Meure et al., 2006]. The reduced sample size requirements as well as automation of a significant portion of the analysis process have enabled me to make >1500 discrete ice core methane measurements and construct the highest resolution records of methane available over the late Holocene. Ice core samples came from the recently completed West Antarctic Ice Sheet (WAIS) Divide ice core which has as one of its primary scientific objectives to produce the highest resolution records of greenhouse gases, and from the Greenland Ice Sheet Project (GISP2) ice core which is a proven paleoclimate archive. My thesis has the following three components. I first used a shallow ice core from WAIS Divide (WDC05A) to produce a 1000 year long methane record with a ~9 year temporal resolution. This record confirmed the existence of multidecadal scale variations that were first observed in the Law Dome, Antarctica ice core. I then explored a range of paleoclimate archives for possible mechanistic connections with methane concentrations on multidecadal timescales. In addition, I present a detailed description of the analytical methods used to obtain high-precision measurements of methane including the effects of solubility and a new chronology for the WDC05A ice core. I found that, in general, the correlations with paleoclimate proxies for temperature and precipitation were low over a range of geographic regions. Of these, the highest correlations were found from 1400-1600 C.E. during the onset of the Little Ice Age and with a drought index in the headwater region of the major East Asian rivers. Large population losses in Asia and the Americas are also coincident with methane concentration decreases indicating that anthropogenic activities may have been impacting multidecadal scale methane variability. In the second component I extended the WAIS Divide record back to 2800 years B.P. and also measured methane from GISP2D over this time interval. These records allowed me to examine the methane Inter-Polar Difference (IPD) which is created by greater northern hemispheric sources. The IPD provides an important constraint on changes in the latitudinal distribution of sources. We used this constraint and an 8-box global methane chemical transport model to examine the Early Anthropogenic Hypothesis which posits that humans began influencing climate thousands of years ago by increasing greenhouse gas emissions and preventing the onset of the next ice age. I found that most of the increase in methane sources over this time came from tropical regions with a smaller contribution coming from the extratropical northern hemisphere. Based on previous modeling estimates of natural methane source changes, I found that the increase in the southern hemisphere tropical methane emissions was likely natural and that the northern hemispheric increase in methane emissions was likely due to anthropogenic activities. These results also provide new constraints on the total magnitude of pre-industrial anthropogenic methane emissions, which I found to be between the high and low estimates that have been previously published in the literature. For the final component of my thesis I assembled a coalition of scientists to investigate the effects of layering on the process of air enclosure in ice at WAIS Divide. Air bubbles are trapped in ice 60-100m below the surface of an ice sheet as snow compacts into solid ice in a region that is known as the Lock-In Zone (LIZ). The details of this process are not known and in the absence of direct measurements previous researchers have assumed it to be a smooth process. This project utilized high-resolution methane and air content measurements as well as density of ice, δ¹⁵N of N₂, and bubble number density measurements to show that air entrapment is affected by high frequency (mm scale) layering in the density of ice within the LIZ. I show that previous parameterizations of the bubble closure process in firn models have not accounted for this variability and present a new parameterization which does. This has implications for interpreting rapid changes in trace gases measured in ice cores since variable bubble closure will impact the smoothing of those records. In particular it is essential to understand the details of this process as new high resolution ice core records from Antarctica and Greenland examine the relative timing between greenhouse gases and rapid climate changes. / Graduation date: 2013

Esta tese interpreta o registro ambiental de um testemunho de gelo antártico pela análise de elementostraço. Esse testemunho de gelo, daqui em diante chamado Mount Johns (MJ), foi coletado no manto de gelo da Antártica Ocidental (79°55’28”S e 94°23’18”W; 91,20 m de comprimento) no verão austral de 2008/09. O testemunho foi descontaminado e subamostrado no Climate Change Institute (University of Maine – Maine /EUA). As primeiras 2137 amostras, correspondentes aos 45 m superiores do testemunho, foram analisadas no espectrômetro de massas Element 2 do CCI para 24 elementos-traço (Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Li, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg e K). Essa parte do testemunho representa 125 anos (1883–2008) de registro, segundo datação relativa baseada na variação sazonal nas concentrações de Na, Sr e S e na identificação dos principais eventos vulcânicos ocorridos no período. A taxa de acumulação média no local de amostragem foi 0,21 m a-1 em eq. H2O no mesmo período de tempo. As concentrações são controladas pelas variações climáticas sazonais (verão/inverno), por mudanças na circulação atmosféricas, por anomalias de temperatura, pela distância de transporte e pelas fontes naturais e antrópicas desses aerossóis. Baseada na análise dos fatores de enriquecimento crustal e marinho e em correlações de Pearson, as concentrações de Al, Ba, Ca, Fe, K, Mg, Mn, Na, S, Sr e Ti são de origem natural. Poeira e solo de fontes continentais, oriundas principalmente de áreas áridas na Austrália, Nova Zelândia e Patagônia, são consideradas importantes fontes de Al, Mg e Ti. Aerossóis marinhos do Pacífico Sul, transportados para o continente antártico pelas massas de ar, são fontes predominantes de Na, Sr, K, S e Ca. Para os elementos Ba, Fe e Mn, tanto fontes crustais como marinhas são significativas. Adicionalmente, Mn e S apresentam um aporte considerável de origem vulcânica (variando de 20–30% na concentração total). Os resultados também mostram enriquecimento significativo nas concentrações de arsênio devido a atividades antrópicas. Foi observado concentrações médias da ordem de 1,92 pg g-1 antes de 1900, aumentando até 7,94 pg g-1 em 1950. Este enriquecimento está diretamente relacionado às emissões da mineração e fundição de metais não-ferrosos na América do Sul, principalmente no Chile. A queda na concentração de arsênio observado no século XXI (concentração média de 1,94 pg g-1 após 1999) é interpretada como uma consequência à introdução de leis ambientais (em 1994) para reduzir emissões desse elemento durante os processos de mineração e fundição de cobre no Chile. O modelo de trajetórias HYSPLIT mostra uma clara variação sazonal no transporte entre os meses de verão/outono e inverno/primavera, onde predomina o transporte de oeste durante o ano todo e um transporte secundário de nordeste durante o verão/outono. As correlações entre as concentrações médias dos elementos-traço estudados e o modelo de reanálises ERA-Interim para o período 1979–2008, indicam que as concentrações de aerossóis marinhos são fortemente influenciadas pelas condições meteorológicas, por exemplo, por anomalias na temperatura da superfície do mar e concentração de gelo marinho. / This thesis interprets the environmental record of an Antarctic ice core by the analysis of trace elements. This ice core, henceforward called Mount Johns (MJ), was collected in the West Antarctica ice sheet (79°55'28"S and 94°23'18"W; 91.20 m long) in the austral summer of 2008/09. The core was decontaminated and subsampled at the Climate Change Institute (CCI, University of Maine - Maine / USA). The first 2137 samples, corresponding to the upper 45 m of the core, were analyzed in the CCI's JRC Element 2 spectrometer for 24 trace elements (Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Li, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg and K). This part of the core represents a 125 years (1883– 2008) record, according to relative dating based on Na, Sr and S seasonal variations and on the identification of major volcanic events in the period. The mean accumulation rate for the sampling site was 0.21 m-1 in eq. H2O in the same time period. The concentrations are controlled by seasonal climatic changes (summer/winter), by changes in atmospheric circulation, temperature anomalies, the transport distance and the natural and anthropogenic sources of these aerosols. Based on analysis of crustal and marine enrichment factors and Pearson correlations, the Al, Ba, Ca, Fe, K, Mg, Mn, Na, S, Sr and Ti concentrations have natural origin. Dust and soil from continental sources, primarily coming from arid areas in Australia, New Zealand and Patagonia, are considered important sources of Al, Mg and Ti. South Pacific marine aerosols, transported to the Antarctic continent by air masses, are predominant sources of Na, Sr, K, S and Ca. For the elements Ba, Fe and Mn, both crustal and marine sources are significant. In addition, Mn and S show a considerable contribution of volcanic origin (ranging from 20-30% of the total concentration). The results also show significant enrichment in arsenic concentrations due to human activities. Before 1900 the mean concentration was approximately 1.92 pg g-1, rising to 7.94 pg g-1 in 1950. This enrichment is directly related to mining emissions and casting of non-ferrous metals in South America, mainly in Chile. The decrease in the arsenic concentration, observed in the twenty-first century (mean concentration of 1.94 pg g-1 after 1999) is interpreted as a consequence of the introduction of environmental laws (in 1994) to reduce emissions of this element during the cupper mining and smelting in Chile. The HYSPLIT trajectories model show a clear seasonal variation in transport between the summer/autumn all and winter/spring months, where predominates an eastward transport throughout the year and a secondary transport from the northeast during the summer/fall. Correlations between the mean concentrations of the studied trace elements and the ERA-Interim reanalysis models for the 1979-2008 period indicate that marine aerosols concentrations are heavily influenced by weather conditions, for example, by sea surface temperature and sea ice concentration anomalies.

Les aérosols atmosphériques jouent un rôle important à la surface de la Terre. Ils influencent les propriétés radiatives de l'atmosphère et représentent des composés importants pour les questions de qualité de l'air et de santé publique dans les régions polluées. Suite à la forte diminution de la pollution soufrée survenue au cours des trois dernières décennies, l'aérosol organique représente maintenant une part importante de l'aérosol atmosphérique. Cette fraction a une nature complexe et jusqu'à présent, moins de la moitié de ses constituants chimiques ont été identifiés. La fraction soluble des HUmic LIke Substances (HULISWS) représente une des familles importantes de l'aérosol organique soluble avec une contribution en masse comprise entre 20 et 50%. L'objectif de cette thèse est de développer une méthode de mesure des HULISWS dans la glace. L'étude de ces archives environnementales, ici une carotte de glace extraite au col du Dôme (4250 m, massif du Mont-Blanc, France), permet de remonter aux concentrations en HULISWS en Europe au cours de la période 1920-1988. L'étude des concentrations et de l'absorbance spécifique des HULISWS dans la carotte de glace a permis d'identifier deux sources distinctes suivant la saison et de suivre leur évolution au cours du XXème siècle. Les HULISWS sont issus de la combustion du bois en hiver, leur absorbance est forte et leurs concentrations sont faibles et stables tout au long du XXème siècle. En été, les HULISWS sont formés par des processus secondaires ayant pour précurseurs des espèces biogéniques organiques, leur absorbance spécifique est plus faible qu'en hiver et leurs concentrations plus fortes. Les teneurs estivales en HULISWS montrent une stabilité entre 1920 et 1950 puis une tendance à l'augmentation entre 1951 et 1970 associée vraisemblablement à une augmentation des émissions de composés organiques volatils depuis la biosphère. / Atmospheric aerosols play an important role on the radiative properties of the atmosphere. They are also key factors for air quality and public health in polluted areas. As a result of the strong decrease of SO2 emissions over the last three decades, organic aerosol now represents a more important part of atmospheric aerosol. The nature of this organic fraction is complex and until now less than a half of it has been chemically identified. Water Soluble HUmic LIke Substances (HULISWS) are an important contributor to water soluble organic aerosol with a mass fraction ranging from 20 to 50%. The aim of this work is to design a method to measure HULISWS in ice cores. The application of this method to an ice core extracted at the col du Dôme (4250 m, Mont-Blanc massif, France) enables to investigate changes in HULISWS over Europe since 1920. The study of their concentrations and specific absorbance in ice core samples reveals well-marked differences in the sources of HULISWS depending on the season. In winter, HULISWS are primarily emitted by wood burning, their specific absorbance is high and their concentrations are low and remained stable over the 20th century. In summer, HULISWS are producted from biogenic precursors by secondary processes, their specific absorbance is lower and their concentrations higher than in winter. Summer concentrations of HULISWS were stable between 1920 and 1950, and have increased from 1951 to 1970. This recent trend probably results from an increase of volatile organic compounds emissions by the biosphere.

Esta tese interpreta o registro ambiental de um testemunho de gelo antártico pela análise de elementostraço. Esse testemunho de gelo, daqui em diante chamado Mount Johns (MJ), foi coletado no manto de gelo da Antártica Ocidental (79°55’28”S e 94°23’18”W; 91,20 m de comprimento) no verão austral de 2008/09. O testemunho foi descontaminado e subamostrado no Climate Change Institute (University of Maine – Maine /EUA). As primeiras 2137 amostras, correspondentes aos 45 m superiores do testemunho, foram analisadas no espectrômetro de massas Element 2 do CCI para 24 elementos-traço (Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Li, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg e K). Essa parte do testemunho representa 125 anos (1883–2008) de registro, segundo datação relativa baseada na variação sazonal nas concentrações de Na, Sr e S e na identificação dos principais eventos vulcânicos ocorridos no período. A taxa de acumulação média no local de amostragem foi 0,21 m a-1 em eq. H2O no mesmo período de tempo. As concentrações são controladas pelas variações climáticas sazonais (verão/inverno), por mudanças na circulação atmosféricas, por anomalias de temperatura, pela distância de transporte e pelas fontes naturais e antrópicas desses aerossóis. Baseada na análise dos fatores de enriquecimento crustal e marinho e em correlações de Pearson, as concentrações de Al, Ba, Ca, Fe, K, Mg, Mn, Na, S, Sr e Ti são de origem natural. Poeira e solo de fontes continentais, oriundas principalmente de áreas áridas na Austrália, Nova Zelândia e Patagônia, são consideradas importantes fontes de Al, Mg e Ti. Aerossóis marinhos do Pacífico Sul, transportados para o continente antártico pelas massas de ar, são fontes predominantes de Na, Sr, K, S e Ca. Para os elementos Ba, Fe e Mn, tanto fontes crustais como marinhas são significativas. Adicionalmente, Mn e S apresentam um aporte considerável de origem vulcânica (variando de 20–30% na concentração total). Os resultados também mostram enriquecimento significativo nas concentrações de arsênio devido a atividades antrópicas. Foi observado concentrações médias da ordem de 1,92 pg g-1 antes de 1900, aumentando até 7,94 pg g-1 em 1950. Este enriquecimento está diretamente relacionado às emissões da mineração e fundição de metais não-ferrosos na América do Sul, principalmente no Chile. A queda na concentração de arsênio observado no século XXI (concentração média de 1,94 pg g-1 após 1999) é interpretada como uma consequência à introdução de leis ambientais (em 1994) para reduzir emissões desse elemento durante os processos de mineração e fundição de cobre no Chile. O modelo de trajetórias HYSPLIT mostra uma clara variação sazonal no transporte entre os meses de verão/outono e inverno/primavera, onde predomina o transporte de oeste durante o ano todo e um transporte secundário de nordeste durante o verão/outono. As correlações entre as concentrações médias dos elementos-traço estudados e o modelo de reanálises ERA-Interim para o período 1979–2008, indicam que as concentrações de aerossóis marinhos são fortemente influenciadas pelas condições meteorológicas, por exemplo, por anomalias na temperatura da superfície do mar e concentração de gelo marinho. / This thesis interprets the environmental record of an Antarctic ice core by the analysis of trace elements. This ice core, henceforward called Mount Johns (MJ), was collected in the West Antarctica ice sheet (79°55'28"S and 94°23'18"W; 91.20 m long) in the austral summer of 2008/09. The core was decontaminated and subsampled at the Climate Change Institute (CCI, University of Maine - Maine / USA). The first 2137 samples, corresponding to the upper 45 m of the core, were analyzed in the CCI's JRC Element 2 spectrometer for 24 trace elements (Sr, Cd, Cs, Ba, La, Ce, Pr, Pb, Bi, U, As, Li, Al, S, Ca, Ti, V, Cr, Mn, Fe, Co, Na, Mg and K). This part of the core represents a 125 years (1883– 2008) record, according to relative dating based on Na, Sr and S seasonal variations and on the identification of major volcanic events in the period. The mean accumulation rate for the sampling site was 0.21 m-1 in eq. H2O in the same time period. The concentrations are controlled by seasonal climatic changes (summer/winter), by changes in atmospheric circulation, temperature anomalies, the transport distance and the natural and anthropogenic sources of these aerosols. Based on analysis of crustal and marine enrichment factors and Pearson correlations, the Al, Ba, Ca, Fe, K, Mg, Mn, Na, S, Sr and Ti concentrations have natural origin. Dust and soil from continental sources, primarily coming from arid areas in Australia, New Zealand and Patagonia, are considered important sources of Al, Mg and Ti. South Pacific marine aerosols, transported to the Antarctic continent by air masses, are predominant sources of Na, Sr, K, S and Ca. For the elements Ba, Fe and Mn, both crustal and marine sources are significant. In addition, Mn and S show a considerable contribution of volcanic origin (ranging from 20-30% of the total concentration). The results also show significant enrichment in arsenic concentrations due to human activities. Before 1900 the mean concentration was approximately 1.92 pg g-1, rising to 7.94 pg g-1 in 1950. This enrichment is directly related to mining emissions and casting of non-ferrous metals in South America, mainly in Chile. The decrease in the arsenic concentration, observed in the twenty-first century (mean concentration of 1.94 pg g-1 after 1999) is interpreted as a consequence of the introduction of environmental laws (in 1994) to reduce emissions of this element during the cupper mining and smelting in Chile. The HYSPLIT trajectories model show a clear seasonal variation in transport between the summer/autumn all and winter/spring months, where predominates an eastward transport throughout the year and a secondary transport from the northeast during the summer/fall. Correlations between the mean concentrations of the studied trace elements and the ERA-Interim reanalysis models for the 1979-2008 period indicate that marine aerosols concentrations are heavily influenced by weather conditions, for example, by sea surface temperature and sea ice concentration anomalies.