Bioremediation and CO2 scavenging using molybdenum-containing enzymes

Carbon dioxide valorization, will not only help to relieve the greenhouse effect but might also allow us to transform it in value-added chemicals that will help overcoming the energy crisis. To accomplish this goal, more research that focus on sequestering CO2 and endeavors through a carbon-neutral or carbon-negative strategy is needed in order to handle with the dwindling fossil fuel supplies and their environmental impact. Formate dehydrogenases are a promising means of turning CO2 into a biofuel that will allow for a reduction of greenhouse gas emissions and for a significant change to the economic paramount. The main objective of this work was to assess whether a NAD+-independent molybdenum-containing formate dehydrogenase is able to catalyze the reduction of CO2 to formate. To achieve this, a molybdenum-containing formate dehydrogenase was isolated from the sulfate reducing bacteria Desulfovibrio desulfuricans ATCC 27774. Growth conditions were found that allowed for a greater cellular mass recovery and formate dehydrogenase expression. After growth trials, kinetic assays for formate oxidation and CO2 reduction were performed and kinetic parameters determined. For the formate oxidation reaction, a KM of 49 μM and a turnover constant of 146 s-1 were determined. These kinetic parameters are in agreement with those determined by Mota, et al. (2011). Finally, we found that this molybdenum-containing enzyme was able to catalyze the reduction of CO2 to formate with a turnover constant of 4.6 s-1 and a KM of 13 μM. For the first time a NAD+-independent molybdenum-containing formate dehydrogenase was found to catalyze CO2 reduction, allowing its use as a biocatalyst in energetically efficient CO2 fixation processes that can be directed towards bioremediation or as an alternative and renewable energy source. Characterizing these enzymes may lead to the development of more efficient synthetic catalysts, make them readily available and more suited for practical applications.

Development and application of NMR techniques to study water-in-CO2 microemulsions

Self-assembly is a phenomenon that occurs frequently throughout the universe. In this work, two self-assembling systems were studied: the formation of reverse micelles in isooctane and in supercritical CO2 (scCO2), and the formation of gels in organic solvents. The goal was the physicochemical study of these systems and the development of an NMR methodology to study them. In this work, AOT was used as a model molecule both to comprehensively study a widely researched system water/AOT/isooctane at different water concentrations and to assess its aggregation in supercritical carbon dioxide at different pressures. In order to do so an NMR methodology was devised, in which it was possible to accurately determine hydrodynamic radius of the micelle (in agreement with DLS measurements) using diffusion ordered spectroscopy (DOSY), the micellar stability and its dynamics. This was mostly assessed by 1H NMR relaxation studies, which allowed to determine correlation times and size of correlating water molecules, which are in agreement with the size of the shell that interacts with the micellar layer. The encapsulation of differently-sized carbohydrates was also studied and allowed to understand the dynamics and stability of the aggregates in such conditions. A W/CO2 microemulsion was prepared using AOT and water in scCO2, with ethanol as cosurfactant. The behaviour of the components of the system at different pressures was assessed and it is likely that above 130 bar reverse microemulsions were achieved. The homogeneity of the system was also determined by NMR. The formation of the gel network by two small molecular organogelators in toluene-d8 was studied by DOSY. A methodology using One-shot DOSY to perform the spectra was designed and applied with success. This yielded an understanding about the role of the solvent and gelator in the aggregation process, as an estimation of the time of gelation.

Assessing the production of jet mix columns using alkali activated waste based on mechanical and financial performance and CO2 (eq) emissions

Recent research has proved the potential of alkaline activated fly-ash for soil stabilisation. However, such studies have not focused on the link between financial, mechanical and environmental aspects of this solution, but only on their absolute mechanical properties. The present paper characterises the mechanical behaviour of a large spectrum of activator-ash-soil combinations used to build jet mixing columns, analysing also the cost and CO2 (eq) emissions. The concern with these two vectors forced a decrease in the quantity of stabilising agent added to the soil, relatively to previous research, and the effects of such low quantities have not yet been published. However, the results clearly showed a significant improve in strength, still well above the average values expected when improving the stressstrain behaviour of a weak soil. Uniaxial compressive strength tests were used to assess the effects of the fly-ash percentage, the alkalieash ratio and the water content. The carbon calculator recently developed by the European Federation of Foundation Contractors and the Deep Foundations Institute was used to quantify the CO2 (eq) emissions associated with this technique. The financial cost was estimated based on the experience of a major Portuguese contractor. For comparison purposes, soil cement mixtures were also analysed, using similar conditions and tools used for the soil-ash analysis. Results showed that the cement and ash solutions are very similar in terms of overall performance, with some advantage of the former regarding financial cost, and a significant advantage of the latter regarding the CO2 (eq) emissions. This new grout, although it is in an embryonic stage, it has the potential for broader developments in the field.

Efluxo de CO2 do solo em floresta de transição Amazônia Cerrado e em área de pastagem

O objetivo deste trabalho foi (a) estimar o efluxo de CO2 do solo em uma Floresta de Transição Amazônica Cerrado e em uma área de Pastagem localizadas no norte do Mato Grosso, e (b) verificar a influência da umidade e temperatura do solo, e serrapilheira acumulada no efluxo de CO2. As medições foram realizadas com aparelho de absorção de CO2 por infravermelho (EGM/WMA-2 PP System, Hitchin Hertz, UK) de maio/2005 a abril/2006. Os valores médios do efluxo de CO2 do solo na Floresta e na área de Pastagem foram de 5,45 e 4,95 µmolm-2s-1, respectivamente. Uma resposta satisfatória do efluxo de CO2 do solo e a serrapilheira acumulada, ocorreu somente na estação seca. Na estação seca o comportamento do efluxo de CO2 do solo foi semelhante na Floresta de Transição Amazônica Cerrado e na área de Pastagem, e na estação úmida os ecossistemas apresentaram comportamentos distintos, e o efluxo de CO2 do solo na área de Pastagem foi superior ao na Floresta de Transição. É essencial que se avalie a influência de outros fatores no efluxo de CO2 em ecossistemas localizados em um mesmo ecótono para a obtenção de novas respostas que contribuíam para esclarecer as dúvidas da emissão de CO2 em nível mundial.

Soil CO2 efflux in central Amazonia: environmental and methodological effects

Soil respiration plays a significant role in the carbon cycle of Amazonian rainforests. Measurements of soil respiration have only been carried out in few places in the Amazon. This study investigated the effects of the method of ring insertion in the soil as well as of rainfall and spatial distribution on CO2 emission in the central Amazon region. The ring insertion effect increased the soil emission about 13-20% for sandy and loamy soils during the firsts 4-7 hours, respectively. After rainfall events below 2 mm, the soil respiration did not change, but for rainfall greater than 3 mm, after 2 hours there was a decrease in soil temperature and respiration of about 10-34% for the loamy and sand soils, with emissions returning to normal after around 15-18 hours. The size of the measurement areas and the spatial distribution of soil respiration were better estimated using the Shuttle Radar Topographic Mission (SRTM) data. The Campina reserve is a mosaic of bare soil, stunted heath forest-SHF and tall heath forest-THF. The estimated total average CO2 emissions from the area was 3.08±0.8 µmol CO2 m-2 s-1. The Cuieiras reserve is another mosaic of plateau, slope, Campinarana and riparian forests and the total average emission from the area was 3.82±0.76 µmol CO2 m-2 s-1. We also found that the main control factor of the soil respiration was soil temperature, with 90% explained by regression analysis. Automated soil respiration datasets are a good tool to improve the technique and increase the reliability of measurements to allow a better understanding of all possible factors driven by soil respiration processes.

Geoquímica de rios de água preta do sudeste do Amazonas: origem, fluxo dos elementos e consumo de CO2

Neste trabalho foi examinada a composição química das águas dos afluentes da margem direita do rio Madeira que drenam as rochas do Escudo Brasileiro. O estudo foi realizado no município de Apuí no sudeste do estado do Amazonas, Brasil. Foram analisados pH, condutividade, as concentrações de SiO2 e de íons dissolvidos (Na+, K+, Mg2+, Ca2+, HCO3-, Cl-, NO3- e SO4(2-)) em quatro épocas do ano segundo o índice pluviométrico: chuvosa, transição para a estiagem, estiagem e transição para a chuvosa. As águas são diluídas, mais concentradas em HCO3- e SiO2 e representam o típico ambiente de intensa lixiviação que afeta as rochas na Amazônia. Apesar da química das águas terem influência da sazonalidade, foram identificadas variações em função da litologia. As taxas de exportação de cátions e de erosão química das rochas são baixas e refletem a estabilidade tectônica da região e o manto intempérico que dificulta a interação da água com o substrato rochoso.

The Proposals for a European tax on CO2 and their implications for intercountry distribution

This paper analyzes the advantages and implications of the implementation of a European tax on carbon dioxide emissions as an own resource of the European Union. In contrast to a harmonized tax, which would only have distributive effects within each member state, a tax collected at European scale would also have important distributive effects among different countries. These effects would also depend on the use of tax revenues. The paper investigates the distributive effects among the member states of three tax models: a pure CO2

Regional decomposition of CO2 emissions in the world: a cluster analysis

The purpose of this paper is to study the possible differences among countries as CO2 emitters and to examine the underlying causes of these differences. The starting point of the analysis is the Kaya identity, which allows us to break down per capita emissions in four components: an index of carbon intensity, transformation efficiency, energy intensity and social wealth. Through a cluster analysis we have identified five groups of countries with different behavior according to these four factors. One significant finding is that these groups are stable for the period analyzed. This suggests that a study based on these components can characterize quite accurately the polluting behavior of individual countries, that is to say, the classification found in the analysis could be used in other studies which look to study the behavior of countries in terms of CO2 emissions in homogeneous groups. In this sense, it supposes an advance over the traditional regional or rich-poor countries classifications .

Inequality in CO2 emissions across countries and its relationship with income inequality: a distributive approach

This paper analyses the inequality in CO2 emissions across countries (and groups of countries) and the relationship of this inequality with income inequality across countries for the period (1971-1999). The research employs the tools that are usually applied in income distribution analysis. The methodology used here gives qualitative and quantitative information on some of the features of the inequalities across countries that are considered most relevant for the design and discussion of policies aimed at mitigating climate change. The paper studies the relationship between CO2 emissions and GDP and shows that income inequality across countries has been followed by an important inequality in the distribution of emissions. This inequality has diminished mildly, although the inequality in emissions across countries ordered in the increasing value of income (inequality between rich and poor countries) has diminished less than the “simple” inequality in emissions. Lastly, the paper shows that the inequality in CO2 emissions is mostly explained by the inequality between groups with different per capita income level. The importance of the inequality within groups of similar per capita income is much lower and has diminished during the period, especially in the low-middle income group.

Análisis de las emisiones de CO2 y sus factores explicativos en las diferentes áreas del mundo

En el presente artículo se analiza la evolución de las emisiones de CO2 –el principal gas de efecto invernadero– en las diferentes áreas del mundo, prestando mayor atención a lo ocurrido en la Unión Europea y España. El análisis se centra especialmente en lo sucedido desde 1990, año de referencia en el protocolo de Kioto para la gran mayoría de países. Se investigan también los principales factores determinantes de las emisiones y su evolución utilizando el análisis de los factores de la identidad de Kaya. El análisis permite explicar las grandes diferencias que se dan entre unas zonas y otras y las distintas variaciones que se ha

Las Propuestas para un impuesto europeo sobre el CO2 y sus potenciales distributivas entre países

En el presente artículo se revisan las propuestas sobre fiscalidad energética y, en concreto, sobre un impuesto europeo que grave las emisiones de dióxido de carbono y las dificultades con que se han encontrado. Se estudian las posibles implicaciones que tendría un impuesto, no ya armonizado, sino recaudado a nivel del conjunto de la Unión Europea. Este tipo de impuesto tendría importantes efectos distributivos no solo a nivel de un país (como un impuesto armonizado) sino también entre diferentes países. El trabajo estudia dichos efectos potenciales según diferentes modelos concretos de implantación (un modelo puro sobre el CO2; un modelo 50%/50% energía-CO2; un modelo puro sobre el CO2 pero gravando también la energía nuclear) y de destino de los fondos recaudados.

An input-output analysis of the "key" sectors in CO2 emissions from a production perspective: an application to the spanish economy

Here we present an approach that allows the identification of the "key" productive sectors responsible for CO2 emission. For this purpose, we develop an input–output methodology from a supply perspective. We focus on the impact of an increase in the value-added of the different productive sectors on total CO2 emissions and we identify the productive sectors responsible for the increase in CO2 emissions when there is an increase in the income of the economy. The approach shows the contribution of the various sectors to CO2 emission from a production perspective and allows us to identify the sectors that deserve more consideration for mitigation policies. This analysis is complementary to the input–output analysis from a demand perspective. The methodology is applied to the Spanish economy.

Análisis de los factores determinantes de las desigualdades internacionales en las emisiones de CO2 per cápita aplicando el enfoque distributivo: una metodología de descomposición por factores de Kaya

En este trabajo desarrollamos una metodología para descomponer las desigualdades internacionales en las emisiones de CO2 en factores (multiplicativos) de Kaya y dos términos de interacción. Utilizamos el índice de desigualdad de Theil y mostramos que esta metodología de descomposición puede extenderse para analizar los componentes de desigualdad inter e intragrupal. A continuación podemos analizar los factores detrás de las desigualdades en las emisiones de CO2 per cápita entre países, entre grupos de países y dentro de los grupos de países. La ilustración empírica sugiere algunas cuestiones. Primero, la desigualdad internacional en las emisiones de CO2 per cápita es principalmente atribuible a las desigualdades en los niveles de renta per cápita, lo que ayuda a explicar su reciente reducción, mientras que las diferencias en la intensidad de carbono de la energía y la intensidad energética han hecho una contribución mucho menos significativa. Este resultado está fuertemente influenciado por el comportamiento de China e India. En segundo lugar, el componente de la desigualdad entre grupos, que es el mayor, está también explicado en buena medida por el factor ingreso. En tercer lugar, el componente de la desigualdad dentro de los grupos aumentó ligeramente durante el período, algo principalmente debido al cambio en el factor de ingreso y los términos de interacción en unas pocas regiones.