It is important to understand the processes that influence the critical zone (CZ) evolution to ensure its sustainability. This thesis reports on laboratory and field experiments designed to measure the behavior of biogenic and lithogenic chemical species and their interaction in the CZ from column to pedon to catchment scales. We postulated that interactions between organic matter and rock-derived metals drive coupled processes of carbon stabilization and chemical weathering and denudation in the Jemez River Basin Critical Zone Observatory (JRB-CZO). First, we observed that secondary mineral coatings (Al and Fe (oxy)hydroxides) on primary silicate surfaces play a major role in sequestering aromatic and "humified" dissolved organic matter (DOM) into sorbate form, significantly retarding their subsurface transport. Further, reinfusion to OM-reacted-porous-media of a different DOM source resulted in exchange reactions consistent with a zonal model of OM adsorption at mineral surfaces. This dissertation also aimed to examine the influence of water and DOM fluxes on the CZ weathering processes. Rare earth elements (REE) were selected because of their coherent trends in reactivity toward organic ligands common to soils. Specifically, trends in REE fractionation were explored for their utility to inform on biogeochemical weathering processes in forested terrain in the JRB-CZO. Mineral weathering mechanisms are expected to differentially influence REE release, fractionation, and transport and the relative importance of such processes should be reflected in REE signatures of bulk soil, pore and surface waters. Our studies showed: (1) REE depletion trends with depth in bulk soils are correlated with topographically-induced variation in water and dissolved organic carbon (DOC) flux (reflected in negative correlations between total water and C fluxes) and solid phase REE concentrations measured at the same depths; (2) REE and DOC concentrations in stream waters were strongly correlated during snowmelt periods of high discharge, consistent with REE complexation and mobilization in association with organic ligands during shallow subsurface flow; (3) preferential sequestration of Eu occurs during formation of secondary Mn(IV)-oxides, explaining patterns of Eu enrichment in bulk soils; and (4) the incremental increase in positive Ce-anomalies with depth in bulk soils are apparently controlled by adsorption/co-precipitation with secondary Fe-(oxy)hydroxide minerals.

Submitted by STELA ROSA AMARAL GONÇALVES (stelinhaamaral@hotmail.com) on 2016-08-12T03:20:24Z No. of bitstreams: 1 Dissertação_final_imai_v3.pdf: 3555316 bytes, checksum: b4386413378a1a29e513286831a880a2 (MD5) / Approved for entry into archive by Ana Paula Grisoto (grisotoana@reitoria.unesp.br) on 2016-08-15T14:30:47Z (GMT) No. of bitstreams: 1 goncalves_sra_me_prud.pdf: 3555316 bytes, checksum: b4386413378a1a29e513286831a880a2 (MD5) / Made available in DSpace on 2016-08-15T14:30:47Z (GMT). No. of bitstreams: 1 goncalves_sra_me_prud.pdf: 3555316 bytes, checksum: b4386413378a1a29e513286831a880a2 (MD5) Previous issue date: 2016-07-08 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Informações quantitativas e qualitativas de sistemas aquáticos podem ser obtidas por meio de dados de sensoriamento remoto. Nesses sistemas, a porção fotoativa do carbono orgânico dissolvido (COD), pode apresentar correlação com o Carbono Orgânico Dissolvido Colorido (CDOM) que é responsável pela alteração da cor da água e consequentemente pode alterar processos de fotossíntese e fotodegradação. Sendo assim o presente trabalho teve como objetivo avaliar a variabilidade espacial das concentrações de CDOM de uma série temporal, de imagens do sensor Operational Land Imager OLI a bordo do satélite Landsat 8, ao longo de um ano no reservatório de Barra Bonita/SP, sendo este o primeiro de uma série de reservatórios em cascata do Rio Tietê, no estado de São Paulo. Foram encontradas correlações entre a concentração laboratorial do COD e o CDOM para o campo de maio o que motivou a modelagem. Foram ajustados modelos inversos, de banda simples e de razão de bandas, para predição de CDOM com dados de dois trabalhos de campo realizados no ano de 2014, sendo o primeiro no mês de maio e o segundo no mês de outubro. Além disso, foram testados modelos encontrados na literatura, também com os dados levantados em campo, para estimativa de CDOM. Os resultados obtidos mostraram que, para os modelos bio-ópticos, de banda simples e razão de bandas, não há diferenças estatistica. O melhor modelo foi selecionado baseado em análise de erro, depois da aplicação dos modelos na imagem OLI coincidente com o trabalho de campo. Uma série de imagens do sensor OLI no período de um ano foi adotada tendo em vista da disponibilidade dos dados gratuitos e resolução radiométrica de 12 bits. A série temporal de imagens do sensor OLI, após ser processada para minimizar os efeitos atmosféricos, permitiu mostrar a dinâmica de CDOM no reservatório em conjunto com dados de precipitação e temperatura do Instituto Nacional de Meteorologia (INMET). Foi possível observar que o reservatório apresenta uma tendência de valores maiores de CDOM após aportes de nutrientes causados por eventos de precipitação. A temperatura apesar de influenciar na velocidade da reação de degradação não foi o fator principal para a variação da concentração de CDOM. O ajuste e avaliação de modelos foi essencial para escolha do modelo mais adequado a realidade local e sazonal do escopo do trabalho. Além disso o modelo aplicado pode contribuir para o cálculo do balanço de carbono, como também em outros estudos que necessitem dessa informação. / Quantitative and qualitative information about aquatic systems can be obtained by using the Remote Sensing techniques. In these aquatic systems, the photoactive portion of Dissolved Organic Carbon (DOC) can be correlated with the Colored Dissolved Organic Matter (CDOM), responsible for the water color alteration and can modify the photosynthesis and photodegradation process. In this sense, this project aimed to evaluate the spatial variability of CDOM concentrations in a one-year temporal analysis from images acquired by the Operational Land Imager OLI sensor onboard the satellite Landsat 8. The study site is the reservoir located in Barra Bonita, State of São Paulo, which is the first in a series of cascading reservoirs from Tietê River in State of São Paulo. The results showed correlations between the COD and CDOM concentrations for the data acquired in May 2014, motivating the CDOM modeling. Inverse models were adjusted, by using simple spectral band and band ratio, for CDOM prediction using data acquired from two field works carried out in 2014, the first in May and the second in October. Moreover, the models found in related literature were tested, also with the data collected in field, for the CDOM estimative. The obtained results showed that for the bio-optical models, from simple spectral band and band ratio, there is no statistic differences. The model who best fitted to the CDOM estimation was selected based on error analysis after their application in OLI images, which coincided with the field work. One year OLI images were used considering their availability, without fees, and their radiometric resolution of 12 bits. This temporal series, after being processed to attenuate the atmospheric effects, allowed showing the CDOM dynamics in the Barra Bonita reservoir combined with temperature and precipitation data from the Instituto Nacional de Metereologia (INMET). It was possible observe that the reservoir shows a bias of higher values of CDOM after nutrients intakes caused by precipitation. The temperature, despite of its influence on degradation reaction velocity, was not the principal factor for the CDOM concentration variation. Finally, the adjustment and models validation was essential for the correct choice of the model which better represents the local and season reality. In addition, the applied model can contribute for the carbon balance calculation, as well for other researches, which use this information.

Les microalgues, qui sont à la base des réseaux trophiques aquatiques, peuvent être la cibleindirecte des herbicides provenant des usages agricoles et urbains. Elles sont également en interaction avecd’autres éléments de leur environnement comme la matière organique dissoute (MOD) naturelle, ellemêmesusceptible d’interagir avec les herbicides. Cette thèse a visé à étudier, en milieu contrôlé, l’influencede la MOD naturelle sur la toxicité d’herbicides vis-à-vis de microalgues en cultures monospécifiques nonaxéniques. Ont été considérés de la MOD naturelle d’eau douce et marine, trois herbicides (irgarol, diuronet S-métolachlore) seuls et en mélange, deux espèces de microalgues dulçaquicoles (Gomphonema gracileet Sphaerellopsis sp.) et deux espèces marines (Chaetoceros calcitrans et Tetraselmis suecica). Les effetsont été déterminés sur la croissance, l’efficacité photosynthétique et le contenu relatif en lipides desmicroalgues. En parallèle, l’environnement chimique a été caractérisé en suivant l’évolution de lacomposition et des propriétés de la MOD, ainsi que des concentrations d’herbicides et de leurs métabolites.Les résultats de ces travaux, qui considèrent pour la première fois la MOD naturelle dans sa globalité eninteraction avec des microalgues et des herbicides, démontrent le rôle clé joué par la MOD sur (i) lastimulation de la croissance des quatre espèces de microalgues (et en retour la modification de la MOD parcelles-ci), (ii) la modulation de la toxicité des herbicides et suggèrent (iii) la capacité de Sphaerellopsis sp.et/ou de ses bactéries associées de biodégrader le diuron. / Microalgae are at the basis of aquatic food webs and may be the indirect target of herbicidesfrom agricultural and urban uses. They also interact with other compounds from their environment such asnatural dissolved organic matter (DOM), which can itself interact with herbicides. This thesis aimed tostudy, in laboratory controlled conditions, the influence of natural DOM on herbicide toxicity to microalgaeby using monospecific, non-axenic cultures. The experiments included: natural freshwater and marineDOM, three herbicides (irgarol, diuron and S-metolachlor) singly and in mixtures, two freshwatermicroalgae (Gomphonema gracile and Sphaerellopsis sp.) and two marine microalgae (Chaetoceroscalcitrans and Tetraselmis suecica). Effects were evaluated on microalgae growth, photosyntheticefficiency and relative lipid content. At the same time, changes in chemical environment over theexperiments were measured through DOM composition and properties, as well as the concentrations inherbicides and their metabolites. The results of this work, which consider for the first time natural DOM asa whole, interacting with microalgae, their associated bacteria and herbicides, demonstrate the key roleplayed by DOM in (i) the growth stimulation of four microalgae (and in return the DOM changes inducedby microalgae), (ii) the modulation of herbicide toxicity and suggest (iii) the ability of Sphaerellopsis sp.and/or its associated bacteria to biodegrade diuron in non-axenic conditions.

En milieu marin, les communautés bactériennes hétérotrophes sont exposées à un mélange hétérogène de composés organiques dissous présentant différents degrés de labilité, qui peuvent contrôler à la fois leurs activités et leur composition. Dans le cadre de cette thèse, nous avons étudié la réponse de communautés bactériennes présentes dans des environnements côtiers contrastés à l’ajout simple ou combiné de différentes sources naturelles de matière organique dissoute (MOD), préalablement photo oxydée ou non et présentant différentes bio réactivités. Dans un premier temps, nous avons étudié l’impact d’ajout de MOD labile provenant de méduses sur l’activité et la diversité bactériennes d’une communauté d’une lagune côtière méditerranéenne. Nous avons observé que la résilience des communautés bactériennes suite à cet ajout était plus importante pour les fonctions métaboliques que pour la diversité. Ceci suggère que les efflorescences de méduses peuvent entrainer des changements durables de la structure des communautés bactériennes en environnement côtier. Dans un deuxième temps, nous nous sommes intéressés à la possibilité d’un priming effect (accélération de la dégradation bactérienne de la MOD réfractaire en présence de MOD labile) en milieu côtier. Des expériences d’ajout simple ou combiné de MOD labile et récalcitrante ont été réalisées sur des communautés bactériennes de Mer Méditerranée et d’un fjord de Patagonie chilienne. Dans les deux cas, nous avons observé des changements plus importants de la composition communautaire bactérienne suite à un ajout combiné. Cependant, nous n’avons pas observé une plus forte consommation de MOD récalcitrante suite à l’ajout de composés labiles, ce qui suggère que le priming effect n’a pas eu lieu au cours de nos expériences. Enfin, nous avons étudié l’impact de la photodégradation de différentes sources de MOD (i.e. MOD récalcitrante de rivière, MOD labile provenant de phytoplancton) sur l’activité et la diversité de communautés bactériennes côtières. Nous avons observé que la photodégradation de la MOD issue d’une culture de phytoplancton entrainait à la fois une croissance bactérienne plus faible et une modification de la diversité bactérienne en faveur des Alphaprotéobactéries. / Heterotrophic bacterial communities in marine environment are exposed to a heterogeneous mixture of dissolved organic compounds with different bioavailability that may control both their activities and their composition. In the frame of this thesis, we studied the response of different coastal bacterial communities to the single or combined addition of various natural dissolved organic matter (DOM) photo-oxidized or not, presenting different bioavailability characteristics. Firstly, we studied the effects of the addition of highly bioreactive DOM derived from jellyfish on bacterial activities and community structure in a Mediterranean coastal lagoon. We observed that resilience of the bacterial community after the addition of DOM from the jellyfish was higher for metabolic functions than diversity, suggesting that jellyfish blooms can induce durable changes in the bacterial community structure in coastal lagoons. Secondly, we investigated the occurrence of priming effect (increase in microbial degradation of refractory DOM upon the addition of labile DOM) on coastal marine environments. Experiments with single or combined additions of recalcitrant and labile DOM sources were performed with a Mediterranean and a Patagonian fjord bacterial communities. In both cases we observed a greater effect of combined addition on bacterial community composition. However we did not observe an increase in recalcitrant DOM degradation of recalcitrant DOM following the addition of labile compounds, suggesting that priming effect did not occur during our experiments. Finally, we studied the impact of contrasted DOM (i.e. recalcitrant riverine DOM, labile phytoplankton-derived DOM) photodegradation on coastal bacterial communities activity and composition. We observed that photodegradation of phytoplankton-derived DOM led to a lower bacterial growth and changes in bacterial community diversity, in favour of Alphaproteobacteria.

Black carbon (BC), the incomplete combustion product from biomass and fossil fuel burning, is ubiquitously found in soils, sediments, ice, water and atmosphere. Because of its polyaromatic molecular characteristic, BC is believed to contribute significantly to the global carbon budget as a slow-cycling, refractory carbon pool. However, the mass balance between global BC generation and accumulation does not match, suggesting a removal mechanism of BC to the active carbon pool, most probable in a dissolved form. The presence of BC in waters as part of the dissolved organic matter (DOM) pool was recently confirmed via ultrahigh resolution mass spectrometry, and dissolved black carbon (DBC), a degradation product of charcoal, was found in marine and coastal environments. However, information on the loadings of DBC in freshwater environments and its global riverine flux from terrestrial systems to the oceans remained unclear. The main objectives of this study were to quantify DBC in diverse aquatic ecosystems and to determine its environmental dynamics. Surface water samples were collected from aquatic environments with a spatially significant global distribution, and DBC concentrations were determined by a chemical oxidation method coupled with HPLC detection. While it was clear that biomass burning was the main sources of BC, the translocation mechanism of BC to the dissolved phase was not well understood. Data from the regional studies and the developed global model revealed a strong positive correlation between DBC and dissolved organic carbon (DOC) dynamics, indicating a co-generation and co-translocation between soil OC and BC. In addition, a DOC-assistant DBC translocation mechanism was identified. Taking advantage of the DOC-DBC correlation model, a global riverine DBC flux to oceans on the order of 26.5 Mt C yr-1 (1 Mt = 1012 g) was determined, accounting for 10.6% of the global DOC flux. The results not only indicated that DOC was an important environmental intermediate for BC transfer and storage, but also provided an estimate of a major missing link in the global BC budget. The ever increasing DBC export caused by global warming will change the marine DOM quality and may have important consequences for carbon cycling in marine ecosystem.

Climate change is causing larger wildfires and more extreme precipitation events throughout the world. As these ecological disturbances increasingly coincide, they are altering lateral fluxes of sediment, organic matter, and nutrients. Increased lateral flux of nutrients could exacerbate eutrophication and associated harmful algal blooms, and increased sediment and organic matter flux could degrade the water supply. Here, we report the immediate stream chemistry response of watersheds in central Utah (USA) that were affected by a megafire followed by an extreme precipitation event in 2018. The wildfires burned throughout the summer of 2018 until the remnants of Hurricane Rosa released torrential rain on the still smoldering, 610-km2 burn scar. To assess how these multiple stressors affected lateral material fluxes, we collected daily to hourly water samples at 10 stream locations starting immediately before the storm event until three weeks after it finished. We quantified suspended sediment, solute and nutrient concentrations, water isotopes, and the concentration, optical properties, and reactivity of dissolved organic matter. For all land-use types, the wildfire caused substantial increases in sediment concentration and flux, increasing total suspended sediment by over 20-fold, attributable to the loss of stabilizing vegetation and increased runoff. Unexpectedly, dissolved organic carbon (DOC) was 2.1-fold higher in burned watersheds, despite the decrease in plant and soil organic matter, and this DOC was 1.3-fold more biodegradable and 2.0-fold more photodegradable than in unburned watersheds based on 28-day light and dark incubations. However, nitrogen and phosphorus concentrations were higher in watersheds with high anthropogenic influences, regardless of burn status. Likewise, direct human land use had a greater effect than wildfire on runoff response, with rapid storm water signals in urban and agricultural areas and a slow arrival of storm water in unburned areas without direct human influence. These findings indicate how megafires and intense rainfall fundamentally increase short-term sediment flux and alter organic matter concentration and characteristics, confirming previous research. These fluxes of degradable dissolved and particulate organic matter could exert short-term pressure on ecosystems already fragmented by human infrastructure. However, in contrast with previous research, which overwhelming focuses on burned-unburned comparisons in pristine watersheds, we found that the presence of urban and agricultural activity exerted a much greater influence on nutrient status than the wildfire. This novel finding suggests that reducing nutrient fluxes from urban and agricultural areas could make ecosystems more resilient to megafire and extreme precipitation events. Together with reducing anthropogenic climate change to reduce the frequency and extent of large wildfires, improving nutrient management should be a priority in semi-arid regions such as Utah.

Freshwater bodies have been long observed to become browner within the northern hemisphere. This brownification, has made drinking water production difficult, since increased organic content in freshwaters requires higher dosages of chemicals during water treatment.  Changes in land use through increased industrial forestry, decreased sulphur deposition from reduced industrial emissions, changing patterns of hydrological and meteorological parameters resulting from climate change, including recently highlighted increase in iron concentrations have been proposed to explain brownification. Drained peat bogs are man-made source of brownifying substances, capable of causing brownification in the rivers and lakes where the water ends up. This research is aimed at investigating dissolved organic matter, total organic carbon, iron, phosphorous, nitrogen and colour in bog ditches draining into the Storån River and Lake Bolmen in southern Sweden, in order to answer these research questions: (1) What are the differences in the level of water quality parameters, pH, conductivity, temperature, DOM, TOC, total phosphorous, total nitrogen, Fe and colour, between bog ditches and Storån River? And what could be the outcome of Colour absorbance comparison, between bog ditches, Storån and lake Bolmen as a single control sample? (2) Is there any association among the different water quality parameters, pH, conductivity, temperature, DOM, TOC, total phosphorous, total nitrogen, Fe and colour within the bog ditch water? Water samples from bog ditches and their corresponding Storån River locations, were used in the analysis. DOM and flow showed significant differences, after statistical test for difference. Conductivity, DOM, total nitrogen and total phosphorous exhibited significant correlations with pH.  TOC also had a correlation with DOM., while colour correlated and depended strongly on Fe, within the bog ditches. Therefore, the bog ditch has behaved to contribute some amount of the brownification, found in Southern Swedish Lakes and Rivers. This knowledge might be useful in future, for more studies and control of Swedish fresh water brownification.

This research combines observation, experimentation, and modeling to evaluate the influence of lakes on dissolved organic matter (DOM) quantity, quality and export in subalpine watersheds of the Sawtooth Mountain Lake District, central Idaho. First, I conducted an empirical study of the hydrologic and biogeochemical controls on DOM dynamics in stream-lake fluvial networks. I hypothesized that lakes would decrease temporal variability (i.e., buffer) and alter the characteristics of DOM from inflow to outflow. I tested these hypotheses by evaluating DOM temporal patterns and measuring annual export in seven-paired lake inflows and outflows. I then evaluated how ultraviolet (UV) exposure affected DOM characteristics during snowmelt and baseflow, and how UV alters baseflow DOM bioavailability and nutrient limitation. Given that increased water residence time increases UV exposure, I hypothesized that lake outflow DOM would be more photorecalcitrant than DOM from lake inflows. I further hypothesized that UV exposure would increase DOM quality, heterotrophic processing, and nutrient demand. Results indicate that lakes can buffer stream temporal variability by acting as a DOM sink during snowmelt and a DOM source during baseflow. Lake outflow DOM photodegradation was similar to lake inflows during snowmelt (p=0.66). Conversely, outflow DOM was 2X more photorecalcitrant than inflow DOM during baseflow (ANOVA, p=0.03) and was strongly related to water residence time (WRT). During baseflow, light exposure increased inflow and outflow DOM bioavailability (p=0.059 and 0.024, respectively) and nutrient limitation (p=0.03 and 0.09, respectively). Combined, these results indicate that WRT in subalpine lakes strongly influences DOM temporal variability and DOM degradation and processing. Thus, lakes can provide temporal stability of DOM and potentially increase both carbon and nutrient uptake by heterotrophs in lake outflows. I then evaluated how global changes could alter hydrologic and nutrient dynamics in a subalpine lake. Model results indicate that the magnitude and timing of snowmelt runoff can have a substantial effect on water and nutrient exports. In phosphorus (P)-limited lakes, increases in inorganic N concentrations within and exported from lakes are likely to occur with increased temperatures and lake WRT. Increases in atmospheric N deposition will further enhance inorganic N exports in P-limited subalpine lakes.

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