The distribution of the partial pressure of surface water CO2 (pCO2sw) was measured throughout the Canadian Arctic Archipelago and Baffin Bay during the summer and fall. Throughout these two seasons, values ranged from 110 μatm and 436 μatm, demonstrating the high level of variability in pCO2sw across the archipelago. Surface waters remained undersaturated compared to atmospheric pCO2 (~386 μatm) for the majority of the sampling period. Generally, areas in which remnant sea ice was melting were observed to be the most undersaturated, whereas warm, ice-free waters in proximity to rivers were supersaturated with respect to atmospheric pCO2. These observations demonstrate how the influence of freshwater from sea ice melt and rivers affect pCO2sw differently. The region was found to act as an overall sink, absorbing on average 17.6 mmol CO2 m-2 day-1 throughout the two seasons. Seasonally specific factors controlling pCO2sw and their effects through a warming climate are discussed.

The Southern Ocean plays a pre-eminent role in the global carbon-climate system. Model studies show that since the start of the preindustrial era, the region has absorbed about 75% of excess heat and 50% of the oceanic uptake and storage (42±5 PgC) of anthropogenic CO2 emissions. However, due to the spatial and seasonal sparseness of the Southern Ocean CO2 observations (biased toward summer), this role is poorly understood. The seasonal sampling biases have hampered observation-based reconstructions of partial pressure of CO2 at the surface ocean (pCO2) using machine learning (ML) and contributed to the convergence of the root mean squared errors (RMSEs) of ML methods to a common limit known in the literature as the “wall”. The hypothesis here is that addressing the critical missing sampling scale will get the community reconstructions of pCO2 “over the wall”. In this study, I explore the sensitivity of pCO2 reconstructions to these observational scale gaps. Using a scale-sensitive sampling strategy means adopting a sampling strategy which addresses these observational limitations including intra-seasonal as well as seasonal sampling aliases in high eddy kinetic energy and mesoscale-intensive regions. In increasing CO2 sampling efforts in the Southern Ocean using autonomous sampling platforms such as floats, Wave Gliders and Saildrones, the community has tried to answer this problem, but the effectiveness of these efforts has not yet been tested. This study aims to do this evaluation and advance our understanding of the sampling scale sensitivities of surface ocean pCO2 reconstructions from machine-learning techniques and contribute – through a scale-sensitive sampling strategy of observing platforms in the Southern Ocean – to breaking through the proverbial “wall”. This aim was achieved through a series of observing system simulation experiments (OSSEs) applied to a forced mesoscale-resolving (±10km) ocean NEMO-PISCES physics-biogeochemistry model with daily output. In addition to underway ships, the sampling scales of the autonomous sampling platforms such as Floats, WaveGliders and Saildrones, on pCO2 reconstructions were investigated in this series of OSSEs. The primary results showed that two sampling scales, which Saildrones are able to address, are required to improve the RMSE scores of machine-learning techniques and then reduce uncertainties and biases in pCO2 reconstructions. The two sampling scales include (1) the seasonal cycle of the meridional gradients and (2) the intra-seasonal variability. Based on the impacts of these two sampling scales on the RMSE scores and biases, it wasfound that resolving the seasonal cycle of the meridional gradient is the first-order requirement while resolving the intra-seasonal variability is the second. Applying the second-order requirement in the whole Southern Ocean to explore the sensitivity of the clustering choice to the two-step pCO2 reconstruction (clustering- regression). It was found that using an ensemble of clustering methods in this two-step reconstruction performs far much better than using a clustering method. Using these findings, I proposed an observational strategy that is viable and strengthens the limitations in existing underway SOCAT ship- and SOCCOM float-based reconstructions of surface ocean pCO2. More specifically, I proposed a hybrid scale-sensitive sampling strategy for the whole Southern Ocean by integrating underway ships with Saildrones on winter lines. The analysis of these multiple OSSEs indicates that improving the pCO2 reconstructions requires scalesensitive data to supplement the underway ship-based observations gridded in the SOCAT product. It was also found that scale-sensitive data consisting of high-resolution observations ( 1 day) extending over the seasonal cycle and capturing the pCO2 meridional gradients results in breaking through the proverbial “wall”. These findings will contribute to an accurate mean annual global carbon budget which is critical for the trend of the ocean sink feedback on global warming as well as ocean acidification.

There is strong evidence that variations in seawater chemistry occurred during the Phanerozoic Eon. Of particular importance are the changes in the Mg2+/Ca2+ ratio because they have been attributed to the oscillations between “calcite” and “aragonite seas” over time. In addition to the Mg2+/Ca2+ ratio variations, there were also major changes in pCO2 levels and alkalinity that could also affect the calcium carbonate (CaCO3) polymorph that precipitates from seawater. Experiments were conducted in seawater where the initial alkalinity and pCO2 levels were varied and then slow degassing of CO2 resulted in a gradual increase of saturation state with respect to CaCO3 and eventually nucleation. The pH was continually monitored throughout the experiments and it was used in combination with the initial alkalinity to calculate the pCO2 and saturation state of aragonite (sigmarag) at the time of nucleation. The morphology and mineralogy of the precipitates were determined using scanning electron microscopy (SEM) and X-ray diffraction (XRD) analysis, respectively. It was observed that the initial alkalinity greatly affected the nucleation pCO2 value and the CaCO3 polymorph that was precipitated. In seawater with Mg2+/Ca2+=1.2 and ~10 mM alkalinity and a pCO2 below 2,500 μatm, calcite that was overgrown with aragonite was the dominate polymorph nucleated, while pure aragonite precipitated when the pCO2 was above 2,500 μatm. Seawater with Mg2+/Ca2+=1.2 and a wide range of initial alkalinities (5-50 mM) produced variable results. Seawater with Mg2+/Ca2+=1.7 produced only aragonite at lower alkalinities, but calcite was nucleated when the alkalinity and pCO2 values were exceptionally high, typically above 11 mM. These results point to the need to also consider the effects of the carbonic acid system in the “critical” Mg2+/Ca2+ region of about 1 to 2 for “calcite seas” and “aragonite seas” at various times throughout the Phanerozoic Eon.

La protection de la grotte ornée de Cussac, inventée en 2000, se base en partie sur la compréhensionde ses relations avec le massif karstique et des conditions d’écoulement dans la zone non saturée deseaux liées à la cavité.Nous bénéficions à Cussac d’un accès à plusieurs écoulements provenant de différentes parties de laZone Non Saturée (ZNS) et d’une petite zone saturée ainsi que de la présence d’une grotte interceptantdes écoulements à l’intérieur du massif. Les paramètres aérologiques de la cavité dont la pressionpartielle de CO2 (pCO2) et la température ont fait l’objet d’un suivi depuis 2003 pour élaborer unmodèle simple de ses relations avec l’atmosphère extérieure et l’atmosphère de la ZNS.Une première partie de l’étude est consacrée à la caractérisation des écoulements par le suivihydrochimique et hydrodynamique depuis 2008. Elle aboutit à un schéma général du fonctionnementdu système karstique perché de Cussac.Au-delà de l’utilisation des outils classiques pour l’étude des aquifères karstiques nous avons souhaitéétudier les écoulements hydrologique et aérologique à travers l’une des spécificités du systèmekarstique : l’interdépendance des phases gazeuse, liquide et solide.Les échanges entre la roche, l’eau et la pCO2 de l’air de la ZNS ont été estimés à partir de l’utilisationdes équations d’équilibre calco-carboniques. Le schéma de fonctionnement est enrichi par une visionconceptuelle des conditions d’écoulement et une localisation dans les différentes parties du massif desprocessus de dissolution et évasion de CO2 et de dissolution et précipitation de carbonate.L’étude du delta13C apporte des précisions sur l’évolution de la pCO2 dans la ZNS et dansl’environnement particulier qu’est la cavité. La signature isotopique du CO2 de la ZNS est estimée àpartir des mesures de delta13C dans les eaux. Cela nécessite de prendre en compte les processusd’évolution du carbone minéral total dissout au cours des écoulements. / The protection of Cussac engraved cave, discovered in 2000, is based upon the comprehension of itsrelationship with the karstic system and flow conditions in the unsaturated zone (UZ) understanding.Cussac site gives access to several springs from different parts of the UZ and a small saturated area.The cave itself is accessible and allows interception of flow inside the karst environment. Aerologicparameters including CO2 partial pressure (pCO2) and temperature of the cave have been monitoredsince 2003 to build a simple model of its relations with external atmosphere air and UZ air.A first part of the work is dedicated to the characterisation of the flows by a monitoring since 2008 ofwater chemistry and dynamics. This part lead to a Cussac perched aquifer functioning general scheme.To complete these classical investigations we wished to define hydrologic and aerologic flows in karstaquifers using one of its specificity: interdependency of gaseous, liquid and solid phases.Exchanges between rock, water and pCO2 of the UZ are estimated using calco-carbonic equilibriumequations. Functioning scheme is enriched by a conceptual view of flow conditions and a localisationin the karst of the CO2 dissolution or evasion and carbonate dissolution or precipitation process.Precisions on pCO2 evolution in UZ and in the particular environment of the cave are given by d13C.Unsaturated Zone CO2 isotopic composition is estimated from d13C measurement in water. This needto take in account total dissolved inorganic carbon variations process.

Atmospheric CO2 emissions are on the rise and are expected to reach 780 parts per million by the year 2100. Research investigating the impacts of increasing CO2 is a relatively new field and the response of phytoplankton communities is largely unknown, especially in coastal and freshwater ecosystems where no CO2 manipulation studies have completed. The present study attempts to encourage uniformity in methods utilized in CO2 perturbation studies and identifies changes in phytoplankton abundance in freshwater (James River) and coastal ocean (Atlantic, Cape Hatteras) sites. A novel bubbling method to manipulate pCO2 was compared with the classic method of acid addition in conjunction with laboratory and in situ experiments. The novel and classic methods were equally effective at manipulating carbonate chemistry to predicted levels. However, the laboratory experiment saw greater variation in both pCO2 levels and chlorophyll-a concentrations throughout the four-day incubation period. The results from the present study encourage use of the novel methodology in combination with in situ experimental setup to assess changes in phytoplankton communities as a result of pCO2 enrichment. This pairing will allow greater replication of small volume incubations without introducing new abiotic conditions such as temperature and light. Additionally this study found no significant treatment effect on phytoplankton communities in either freshwater James River or coastal Atlantic.

Studies have concluded that streams emit CO2, which indicates that natural sources of Greenhouse Gases can contribute to climate changefeedback. Why this is of interest is to be able to make reliable climate models. These studies are however debated, since there are differentmethods to measure CO2 evasion from streams which conclude that different hydrological and chemical factors are affecting the gas exchange themost. It is based on an upside-down-placed chamber in the streams, containing a sensor which is able to directly measure the partial pressure ofCO2 (pCO2) in streams. An advantage with this method is that it is built on cheap equipment and therefore can be afforded to cover a bigcatchment with differing hydrological factors. The aim for the thesis is to evaluate the usefulness of this new method by running several statisticalanalyses on the collected data and also by comparing the trend from the statistical results to other methods statistical trends of pCO2. What can beconcluded by this study is that discharge affects the pCO2 in streams and it often appears with a negative correlation. Also, diurnal patterns ofpCO2 seem to appear, with a peak before lunch and minimum levels in the afternoon, which could indicate that pCO2 are dependent onphotosynthesis/respiration and/or temperature. These conclusions are of interest to understand how C acts in freshwater and respond to the climatechange. The study has to be extended with investigation of how more factors affect pCO2 and also some improvement for the method, before itcan be fully used. / Forskning har visat att små skogsbäckar släpper ut CO2 och på så sätt bidrar de till naturliga utsläpp av växthusgaser ochklimatförändringar. Studiernas resultat är dock debatterade då de till att börja med används olika metoder för att dra dessa slutsatser,vilka pekar på både olika kvantiter av CO2 utsläpp och också på olika påverkan från hydrologiska och kemiska faktorer. På grund avdetta har en alldeles ny metod utvecklats. Den grundar sig på en uppochnervänd kammare placerad i vatten som med hjälp av eninbyggd sensor fångar upp och mäter partialtrycket CO2 (pCO2) i vattnet. En fördel är att den är byggd av enkelt material til l lågt pris,vilket gör att metoden kan användas på många platser samtidigt, då man har råd med ett stort antal kammare. Målet för avhandlingenär att utvärdera nyttan av denna nya metod genom att köra flera statistiska analyser på de insamlade uppgifterna och även genom attjämföra utvecklingen från statistiska resultaten till andra metoder statistiska trender av pCO2. Studien kan visa att vattenhastighetenpåverkar pCO2 från bäckarna, och korrelationens struktur är betydande på vattennivån i bäcken. Man kan även dra slutsatser om attdet finns en dygnsrytm i hur CO2 släpps ut från bäckar med högsta utsläpp under förmiddagen och lägsta på eftermiddagen. Dettaskulle kunna bero på att CO2 utsläpp beror på fotosyntes/respiration och/eller temperaturskillnader. Dessa slutsatser är väldigtintressanta för att bygga på kunskapen om hur kolemissioner från sötvatten påverkas av klimatförändringarna. Om man utökar studienmed fler möjliga variabler för att studera hur andra miljöfaktorer påverkas pCO2 och modifiera metoden och datainsamlandet något såkan detta vara en metod värd att fortsätta användas.

Carbon dioxide is the primary driver of dissolution and precipitation reactions in epigene limestone caves. While much work has been conducted on CO2 dynamics involved in dissolution in the phreatic zone, less research has been conducted on vadose CO2 dynamics, especially in tropical caves developed in eogenetic limestones. In this study, we investigate spatial and temporal variation in pCO2 in the deep vadose zone of eogenetic limestone above Jinapsan Cave, located in northern Guam. Five years of carbonate chemistry data from three dripwater sites in Jinapsan Cave (Flatman, Station1, and Trinity) were used to model the theoretical pCO2 with which infiltrating waters had likely equilibrated along flow paths between the soil and the cave. Theoretical pCO2 essentially models the amount of CO2 that would need to be added to dripwaters that have degassed and become supersaturated with respect to calcite upon entering a lower CO2 cave void in order to return the water to equilibrium. Theoretical pCO2 values range from 10-2.8 to 10-1.8 atm among the three sites examined. These results were generally lower compared to similar studies in telogenetic and continental karst, which range from 10-3.7 to 10-0.96 atm. Theoretical pCO2 data from Jinapsan Cave have significant differences among the three drip sites, with the site closest to the entrance (Flatman) having the highest values and the farthest from the entrance (Trinity) having the lowest values; in addition, the values also have a great seasonal variability. Low theoretical pCO2 values in Jinapsan Cave’s dripwaters indicate that vadose zones in eogenetic limestone may be better ventilated, and hence have lower pCO2, than those in telogenetic limestone. The ventilation of the vadose zone is facilitated by high matrix porosity and permeability of eogenetic limestone and may be driven by barometric pressure changes or wind.

Phreatic overgrowths on speleothems (POS) are one of many sea-level proxies available to Quaternary geologists in Mallorca; these carbonate encrustations form at the air-water interface in cave passages flooded with brackish water. POS are ideal for reconstruction of western Mediterranean sea level because they are widespread in Mallorca's caves, can be precisely dated by U-series methods, constrain sea-level stands to sub-meter elevation, and are well preserved and accessible in the subterranean environment. This research investigates the POS depositional environment, which is relatively understudied compared to the other proxies used for sea-level reconstructions. This disparity has led to assumptions on many aspects of the POS precipitation. Further, POS are typically composed of calcite, but sometimes the metastable polymorph aragonite is present instead. Two caves were studied because of the presence of a modern POS horizon of aragonite and calcite: Cova des Pas de Vallgornera (Vallgornera) and Coves del Drac (Drac), respectively. High-resolution air and water physical parameters were collected for the first time, along with monthly water samples for stable isotope and elemental analysis. This 16-month record was supplemented with detailed geochemical studies throughout the project, including water-column profiles and CO2 sampling campaigns. The water level in both caves preserves the semi-diurnal Mediterranean Sea tide signal, with a lag of approximately four hours. The fluctuation in both caves is slightly attenuated, and the direct effects of barometric pressure and precipitation could not be discerned from the primary control of tidal pumping. Calculations based on salinity and isotope analysis show that less than 20% of the solution in each cave is seawater. Degassing of CO2 from the cave water to air was documented at both locations, with sporadic calcium carbonate supersaturation. These conditions are strongly dependent on annual cave ventilation, which becomes active during winter when cold, dense tropospheric air sinks into the subsurface. In addition to seasonal thermo-circulation, fluctuating water level displaces cave air and likely initiates tropospheric exchange throughout the year. This process primarily occurs through fissures in thin overlying bedrock at Vallgornera and through the large entrance in Drac. Higher elemental ratios (Mg:Ca, Sr:Ca, Mg:Sr) known to enhance aragonite precipitation or inhibit calcite precipitation were recorded in Vallgornera's water. A linear correlation with salinity was not observed, so higher ratios in Vallgornera must be contributed from differences in lithology, bedrock weathering intensity, or nearby rising thermal waters. In summary, this research confirms POS strengths as sea-level proxies from geochemical and hydrological perspectives. These carbonate encrustations are precipitated at the air-water interface, which fluctuates as an attenuated expression of Mediterranean Sea tide. Degassing of CO2 from the cave water to air, which promotes calcium carbonate supersaturation, is the major control on POS deposition, and is facilitated by winter ventilation and likely water-level fluctuations. CO2 degassing (and theoretically precipitation of POS) in isotopic equilibrium is possible in caves with restricted ventilation (small/sealed entrances, small passages). Aragonite may be precipitated instead of calcite because of local modifications to the geochemical system from bedrock weathering or contributions from deep groundwater.

<p>This dissertation identifies and quantifies the impact of processes driving two biogeochemical phenomena of interest by considering them in the context of the large-scale circulation in which they occur. Both processes occur in the North Pacific transition zone (NPTZ), a basin-wide region near the subpolar-subtropical gyre boundary. </p><p>First, this work investigates the physical forcing behind the large seasonal variability in the location of the Transition zone chlorophyll front (TZCF). The TZCF is a persistent gradient in sea surface color that separates high chlorophyll waters to the north from low chlorophyll waters to the south. The chlorophyll front shifts seasonally by about 1000 km, oscillating between its southernmost winter latitude and its northernmost summer latitude. The forcing behind this seasonal signal is of interest because a number of migratory marine animals, both commercial and endangered, appear to track it.</p><p>This first study finds that vertical processes, traditionally viewed as controlling the dynamical supply of nutrients to surface waters, are insufficient to explain seasonal variations in nutrient supply to the transition zone. Instead, the wind-driven horizontal Ekman transport of nutrients, moving southward from the subpolar gyre into the northern reaches of the subtropical gyre, drives the southward migration of the TZCF. Such lateral transport of nitrate supports up to 40% of new primary productivity in the region annually, and nearly all of new primary productivity in the winter. </p><p>Second, this work investigates why the North Pacific transition zone waters are a notably strong sink for atmospheric carbon dioxide (CO2) on a mean annual basis, while seasonally they vary from a sink in the winter to a neutral to weak source in the summer. As the partial pressure of carbon dioxide (pCO2) in the surface mixed layer exerts primary control on the direction and magnitude of air-sea carbon exchange, this study quantifies the impact of processes regulating seawater pCO2: temperature, salinity, advection of dissolved inorganic carbon (DIC) and alkalinity (ALK), mixing of DIC and ALK, biology, and air-sea carbon flux.</p><p>Seasonal controls on pCO2 in the North Pacific transition zone differ from annual controls. Temperature effects dominate the seasonal signal, but are partially countered throughout the year by opposing processes. In spring and summer, biological drawdown partially offsets the increase in pCO2 due to warming waters; in fall and winter, the vertical entrainment of carbon moderates the decrease in pCO2 due to cooling waters. On a mean annual basis, air-sea carbon flux, biology, mixing, and advection all have a net impact on seawater pCO2. Though important seasonally, temperature has a small impact on pCO2 and air-sea carbon flux annually, accounting for only about 15-20% of oceanic carbon uptake through temperature-driven solubility changes.</p><p>This second study again finds an important role for lateral processes to play in regulating biogeochemical phenomena in the North Pacific transition zone. The ability of the region to uptake atmospheric carbon year after year is maintained by those processes exporting carbon from its surface waters: the vertical export of organic carbon to depth, and the lateral geostrophic advection of carbon out of the region. This lateral advection alone determines the location of the sink region: of the processes impacting seawater pCO2 on a mean annual basis, only the geostrophic divergence of DIC disproportionately lowers pCO2 in the transition zone latitudes, supporting greater atmospheric CO2 uptake here than in surrounding regions.</p><p>This dissertation identifies and quantifies processes driving biogeochemical features in the North Pacific transition zone, finding the large-scale circulation in the region plays a significant role in regulating these processes. The unique physical oceanographic characteristics of the NPTZ, and in particular the lateral transport, support biological and chemical attributes notably distinct from adjacent waters.</p> / Dissertation

Made available in DSpace on 2014-12-17T15:03:34Z (GMT). No. of bitstreams: 1 JurandirRMJ_DISSERT.pdf: 1054152 bytes, checksum: 95f074a057b6d2e03d6f4a8700465d95 (MD5) Previous issue date: 2014-03-31 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / The aquatic ecosystems can play a role as carbon-dioxide-source or carbon-dioxide-sink systems due to the high predominance of heterotrophic or autotrophic metabolism. The primary production can strongly affect the carbon balance (CO2) through the consumption of carbon dioxide in the photosynthesis, especially in eutrophic environment, acting as a carbon sink. The present study tested the hypothesis that the eutrophic reservoirs in tropical semi-arid region are carbon dioxide-sink systems due to the high primary productivity presented in these systems. Five Brazilian reservoirs from the semi-arid in the northeast region were monitored monthly during four years (2010 to 2013) with a prolonged drought event identified during the study. The results showed an increasing level of eutrophication over the period of prolonged drought, with the predominance of autotrophy. Significant negative correlations were observed between the partial pressure of CO2 (pCO2) (p<0,001) and chlorophyll-a in the Boqueir?o, Passagem das Tra?ras, Dourado and Gargalheiras reservoirs, showing a pattern of the carbon dioxide-sink systems. However, this pattern was not found in Cruzeta reservoir. In summary, in the tropical semi-arid region, hydrological and morphometric variables can lead to different behaviors of the water-supply reservoirs on the carbon metabolism. The eutrophic reservoirs evaluated showed a negative relationship between pCO2 and Chl-a, which suggests that these water bodies show an autotrophic metabolism and behave as carbon dioxide- sink systems / Os ecossistemas aqu?ticos podem atuar como emissores ou sequestradores de carbono em fun??o da predomin?ncia do metabolismo heterotr?fico ou autotr?fico. A produ??o prim?ria pode afetar fortemente o balan?o de carbono (CO2) atrav?s do consumo de di?xido de carbono na fotoss?ntese, especialmente em ambiente eutr?ficos, atuando como sumidouros. O presente estudo testou a hip?tese de que reservat?rios eutrofizados da regi?o tropical semi?rida s?o sequestradores de CO2 em fun??o da alta produtividade evidenciada nesses sistemas. Cinco reservat?rios da regi?o semi?rida do nordeste do Brasil foram monitorados mensalmente durante o per?odo de 2010 ? 2013, com um evento de seca prolongada identificado durante o estudo. Os resultados mostraram um crescente n?vel de eutrofiza??o ao longo do per?odo de seca prolongada com predomin?ncia de autotrofia. Foram observadas correla??es negativas significativas entre a press?o parcial de CO2 (pCO2) (p<0,001) e clorofila-a nos reservat?rios Boqueir?o, Passagem das Tra?ras, Dourado e Gargalheiras, evidenciando um padr?o de sequestro de CO2 desses sistemas. Por?m, este padr?o n?o foi encontrado no reservat?rio Cruzeta. Em s?ntese, na regi?o semi?rida tropical, as vari?veis hidrol?gicas e morfom?tricas podem direcionar diferentes comportamentos dos reservat?rios de abastecimento no metabolismo do carbono. Os reservat?rios eutrofizados avaliados apresentaram uma rela??o negativa entre pCO2 e Chl-a o que sugere que estes corpos h?dricos evidenciam um metabolismo autotr?fico e se comportam como sequestradores de CO2