Composition and stability of organic matter fractions in soils under different land use regimes

Soil organic matter (SOM) vitally impacts all soil functions and plays a key role in the global carbon (C) cycle. More than 70% of the terrestric C stocks that participate in the active C cycle are stored in the soil. Therefore, quantitative knowledge of the rates of C incorporation into SOM fractions of different residence time is crucial to understand and predict the sequestration and stabilization of soil organic carbon (SOC). Consequently, there is a need of fractionation procedures that are capable of isolating functionally SOM fractions, i.e. fractions that are defined by their stability. The literature generally refers to three main mechanisms of SOM stabilization: protection of SOM from decomposition by (i) its structural composition, i.e. recalcitrance, (ii) spatial inaccessibility and/or (iii) interaction with soil minerals and metal ions. One of the difficulties in developing fractionation procedures for the isolation of functional SOM fractions is the marked heterogeneity of the soil environment with its various stabilization mechanisms – often several mechanisms operating simultaneously – in soils and soil horizons of different texture and mineralogy. The overall objective of the present thesis was to evaluate present fractionation techniques and to get a better understanding of the factors of SOM sequestration and stabilization. The first part of this study is attended to the structural composition of SOM. Using 13C cross-polarization magic-angle spinning (CPMAS) nuclear magnetic resonance (NMR) spectroscopy, (i) the effect of land use on SOM composition was investigated and (ii) examined whether SOM composition contributes to the different stability of SOM in density and aggregate fractions. The second part of the present work deals with the mineral-associated SOM fraction. The aim was (iii) to evaluate the suitability of chemical fractionation procedures used in the literature for the isolation of stable SOM pools (stepwise hydrolysis, treatments using oxidizing agents like Na2S2O8, H2O2, and NaOCl as well as demineralization of the residue obtained by the NaOCl treatment using HF (NaOCl+HF)) by pool sizes, 13C and 14C data. Further, (iv) the isolated SOM fractions were compared to the inert organic matter (IOM) pool obtained for the investigated soils using the Rothamsted Carbon Model and isotope data in order to see whether the tested chemical fractionation methods produce SOM fractions capable to represent this pool. Besides chemical fractionation, (v) the suitability of thermal oxidation at different temperatures for obtaining stable SOC pools was evaluated. Finally, (vi) the short-term aggregate dynamics and the factors that impact macroaggregate formation and C stabilization were investigated by means of an incubation study using treatments with and without application of 15N labeled maize straw of different degradability (leaves and coarse roots). All treatments were conducted with and without the addition of fungicide. Two study sites with different soil properties and land managements were chosen for these investigations. The first one, located at Rotthalmünster, is a Stagnic Luvisol (silty loam) under different land use regimes. The Ah horizons of a spruce forest and continuous grassland and the Ap and E horizons of two plots with arable crops (continuous maize and wheat cropping) were examined. The soil of the second study site, located at Halle, is a Haplic Phaeozem (loamy sand) where the Ap horizons of two plots with arable crops (continuous maize and rye cropping) were investigated. Both study sites had a C3-/C4-vegetational change on the maize plot for the purpose of tracing the incorporation of the younger, maize-derived C into different SOM fractions and the calculation of apparent C turnover times of these. The Halle site is located near a train station and industrial areas, which caused a contamination with high amounts of fossil C. The investigation of aggregate and density fractions by 13C CPMAS NMR spectroscopy revealed that density fractionation isolated SOM fractions of different composition. The consumption of a considerable part (10–20%) of the easily available O-alkyl-C and the selective preservation of the more recalcitrant alkyl-C when passing from litter to the different particulate organic matter (POM) fractions suggest that density fractionation was able to isolate SOM fractions with different degrees of decomposition. The spectra of the aggregate fractions resembled those of the mineral-associated SOM fraction obtained by density fractionation and no considerable differences were observed between aggregate size classes. Comparison of plant litter, density and aggregate size fractions from soil under different land use showed that the type of land use markedly influenced the composition of SOM. While SOM of the acid forest soil was characterized by a large content (> 50%) of POM, which contained high amounts of spruce-litter derived alkyl-C, the organic matter in the biologically more active grassland and arable soils was dominated by mineral-associated SOM (> 95%). This SOM fraction comprised greater proportions of aryl- and carbonyl-C and is considered to contain a higher amount of microbially-derived organic substances. Land use can alter both, structure and stability of SOM fractions. All applied chemical treatments induced considerable SOC losses (> 70–95% of mineral-associated SOM) in the investigated soils. The proportion of residual C after chemical fractionation was largest in the arable Ap and E horizons and increased with decreasing C content in the initial SOC after stepwise hydrolysis as well as after the oxidative treatments with H2O2 and Na2S2O8. This can be expected for a functional stable pool of SOM, because it is assumed that the more easily available part of SOC is consumed first if C inputs decrease. All chemical treatments led to a preferential loss of the younger, maize-derived SOC, but this was most pronounced after the treatments with Na2S2O8 and H2O2. After all chemical fractionations, the mean 14C ages of SOC were higher than in the mineral-associated SOM fraction for both study sites and increased in the order: NaOCl < NaOCl+HF ≤ stepwise hydrolysis << H2O2 ≈ Na2S2O8. The results suggest that all treatments were capable of isolating a more stable SOM fraction, but the treatments with H2O2 and Na2S2O8 were the most efficient ones. However, none of the chemical fractionation methods was able to fit the IOM pool calculated using the Rothamsted Carbon Model and isotope data. In the evaluation of thermal oxidation for obtaining stable C fractions, SOC losses increased with temperature from 24–48% (200°C) to 100% (500°C). In the Halle maize Ap horizon, losses of the young, maize-derived C were considerably higher than losses of the older C3-derived C, leading to an increase in the apparent C turnover time from 220 years in mineral-associated SOC to 1158 years after thermal oxidation at 300°C. Most likely, the preferential loss of maize-derived C in the Halle soil was caused by the presence of the high amounts of fossil C mentioned above, which make up a relatively large thermally stable C3-C pool in this soil. This agrees with lower overall SOC losses for the Halle Ap horizon compared to the Rotthalmünster Ap horizon. In the Rotthalmünster soil only slightly more maize-derived than C3-derived SOC was removed by thermal oxidation. Apparent C turnover times increased slightly from 58 years in mineral-associated SOC to 77 years after thermal oxidation at 300°C in the Rotthalmünster Ap and from 151 to 247 years in the Rotthalmünster E horizon. This led to the conclusion that thermal oxidation of SOM was not capable of isolating SOM fractions of considerably higher stability. The incubation experiment showed that macroaggregates develop rapidly after the addition of easily available plant residues. Within the first four weeks of incubation, the maximum aggregation was reached in all treatments without addition of fungicide. The formation of water-stable macroaggregates was related to the size of the microbial biomass pool and its activity. Furthermore, fungi were found to be crucial for the development of soil macroaggregates as the formation of water-stable macroaggregates was significantly delayed in the fungicide treated soils. The C concentration in the obtained aggregate fractions decreased with decreasing aggregate size class, which is in line with the aggregate hierarchy postulated by several authors for soils with SOM as the major binding agent. Macroaggregation involved incorporation of large amounts maize-derived organic matter, but macroaggregates did not play the most important role in the stabilization of maize-derived SOM, because of their relatively low amount (less than 10% of the soil mass). Furthermore, the maize-derived organic matter was quickly incorporated into all aggregate size classes. The microaggregate fraction stored the largest quantities of maize-derived C and N – up to 70% of the residual maize-C and -N were stored in this fraction.

Water Resource Pollution and Impacts on the local livelihood: A case study of Beas River in Kullu District, India

The rivers are considered as the life line of any country since they make water available for our domestic, industrial and recreational functions. The quality of river water signifies the health status and hygienic aspects of a particular region, but the quality of these life lines is continuously deteriorating due to discharge of sewage, garbage and industrial effluents into them. Thrust on water demand has increased manifolds due to the increased population, therefore tangible efforts to make the water sources free from pollution is catching attention all across the globe. This paper attempts to highlight the trends in water quality change of River Beas, right from Manali to Larji in India. This is an important river in the state of Himachal Pradesh and caters to the need of water for Manali and Kullu townships, besides other surrounding rural areas. The Manali-Larji Beas river stretch is exposed to the flow of sewage, garbage and muck resulting from various project activities, thereby making it vulnerable to pollution. In addition, the influx of thousands of tourists to these towns also contributes to the pollution load by their recreational and other tourist related activities. Pollution of this river has ultimately affected the livelihood of local population in this region. Hence, water quality monitoring was carried out for the said stretch between January, 2010 and January, 2012 at 15 various locations on quarterly basis, right from the upstream of Manali town and up to downstream of Larji dam. Temperature, color, odor, D.O. , pH, BOD, TSS, TC and FC has been the parameters that were studied. This study gives the broad idea about the characteristics of water at locations in the said river stretch, and suggestions for improving water quality and livelihood of local population in this particular domain.

Implementación de buenas prácticas logísticas en el marco de seguridad industrial, almacenamiento y gestión del control de inventarios en la empresa Yokomotos

Con este trabajo se pretende generar una implementación de una mejora logística que agregue valor, aumente la eficiencia y mejore los procesos de almacenamiento y distribución, gestión del control de inventarios y seguridad industrial de la empresa YOKOMOTOS. Se realizó un estudio profundo de la situación y los problemas que tiene actualmente la empresa. Todo esto con el fin de dar resultados que diferencien a esta compañía en el mercado de los repuestos para motos, obteniendo mayor prestigio y reconocimiento a nivel latinoamericano. De igual forma se establecieron las posibles soluciones que permitieran mitigar estos problemas, mejorando los procesos en el área de almacenamiento, sistema de inventarios y seguridad industrial. Se realizaron diferentes pruebas piloto para analizar la viabilidad de nuestras soluciones, analizando espacios, tiempos y costos. Por último se implementó la mejor solución la cual se ajustó respondiendo a los requerimientos de la compañía, mejorando así los procesos de almacenamiento y distribución agregándole valor a su cadena.

Capacidades dinámicas; la fuente de sostenibilidad ante el cambio

Las capacidades dinámicas constituyen un aporte importante a la estrategia empresarial. De acuerdo con esta premisa se desarrolla el siguiente documento, al reconocer que la generación de competencias se consolida como la base teórica para el logro de sostenibilidad ante eventos de cambio que puedan afectar la estabilidad y la toma de decisiones de las organizaciones. Dada la falta de aplicación empírica del concepto se ha elaborado este paper, en el que se demuestran e identifican las herramientas que la aplicación empiríca puede dar a las organizaciones y los instrumentos que proveen para la generación de valor. A través del caso de estudio ASOS.COM se ejemplifica la necesidad de detección y aprovechamiento de oportunidades y amenazas, así como la reconfiguración, renovación y generación de competencias de segundo orden para enfrentar el cambio. De esta manera por medio de las habilidades creadas al interior de las empresas con enfoque en el aprendizaje e innovación se logra la comprensión del negocio y el afianzamiento de mejores escenarios futuros.

Niveles de exposición ambiental a polvo de carbón y su relación con las condiciones de higiene y seguridad industrial en trabajadores de minas subterráneas de la región de Boyacá

Introducción: La minería subterránea es considerada de alto riesgo afectando la salud de trabajadores expuestos a factores de riesgo y condiciones de trabajo, sin que exista información sobre concentración de material particulado y niveles de riesgo. Objetivo: Determinar la exposición ambiental a polvo de carbón y su relación con las condiciones de higiene y seguridad industrial en los trabajadores que laboran en minas subterráneas de la región de Boyacá. Materiales y métodos: Estudio de corte transversal donde se emplearon cuestionarios para recolectar datos sobre condiciones de trabajo y se realizaron muestreos ambientales de material particulado mediante método de análisis gravimétrico y metodología 0600 de NIOSH. Resultados: Estudio realizado en 19 empresas con 232 trabajadores, con edades entre 20 y 73 años. La concentración promedio de material particulado en los 209 monitoreos realizados fue de 3,4 +3,4mg/m3. El nivel de riesgo alto por exposición a polvo de carbón se encontró en el 70,8% (148) de los monitoreos y el 20,6% (43) en nivel severo, con promedio de 4,9 +4,9 mg/m3. Asociaciones significativas se reportaron entre trabajadores que no usaban protección respiratoria y nivel de riesgo medio y alto (p=0,033); uso mascarilla sin cartucho y nivel de riesgo bajo y medio (p=0,013); el no uso de protección auditiva y niveles medio y alto (p=0,010) y consumo de cigarrillo en el trabajo y niveles medio, alto y severo (p=0,008). Conclusiones: Se determinó vinculación y relación significativa entre los niveles de riesgo alto y severo por exposición a polvo de carbón con concentraciones por encima de niveles permisibles y las condiciones de seguridad industrial de trabajadores

Prevalencia de neumoconiosis y su relación con medidas de higiene y seguridad industrial y niveles ambientales de carbón en minería subterránea en el departamento de Cundinamarca - Colombia, 2015

Introducción: La exposición en minas subterráneas a altos niveles de polvo de carbón está relacionada con patologías pulmonares. Objetivo: Determinar la prevalencia de neumoconiosis, medidas de higiene y seguridad industrial y su relación con niveles ambientales de carbón en trabajadores de minas de socavón en Cundinamarca. Materiales y Métodos: Estudio de corte transversal, en 215 trabajadores seleccionados mediante muestreo probabilístico estratificado con asignación proporcional. Se realizaron monitoreos ambientales, radiografías de tórax y encuestas con variables sociodemográficas y laborales. Se emplearon medidas de tendencia central y dispersión y la prueba de independencia ji-cuadrado de Pearson o pruebas exactas, con el fin de establecer las asociaciones. Resultados: El 99,5% de la población perteneció al género masculino, el 36,7% tenía entre 41-50 años, con un promedio de años de trabajo de 21,70 ± 9,99. La prevalencia de neumoconiosis fue de 42,3% y la mediana de la concentración de polvo de carbón bituminoso fue de 2,329670 mg/m3. El índice de riesgo de polvo de carbón presentó diferencias significativas en las categorías de bajo (p=0,0001) y medio (p=0,0186) con la prevalencia de neumoconiosis. El 84,2% reporto no usar mascarilla. No se presentan diferencias entre los niveles de carbón (p=0,194) con la prevalencia de neumoconiosis. Conclusiones: Se encontró una prevalencia de neumoconiosis de 42,3% en Cundinamarca. Se requiere contar con medidas de higiene y seguridad industrial efectivas para controlar el riesgo al que están expuestos los mineros de carbón por la inhalación de polvo de carbón.

Productivity, demand and the home market effect

The causality between international trade and industrialization is still ambiguous. We consider a model of international trade with the Home Market Effect - with differences in income and productivity between sectors and between countries - in order to identify additional channels for determining the effects of international trade on industrialization. Introducing non-homothetic preferences and differences in productivity aids in the interpretation of any apparent paradoxes within international trade, such as the commercial relations between more populated countries like China and India and large economies such as the U.S. Population size, demand composition and productivity levels constitute the three main channels for determining the effects of international trade. Interactions among these channels define the results obtained in terms of industrialization, while welfare levels are always higher in relation to autarky.

Rhodium(I) catalyzed [2+2+2] cycloaddition reactions: experimental and theoretical studies

The [2+2+2] cycloaddition reaction involves the formation of three carbon-carbon bonds in one single step using alkynes, alkenes, nitriles, carbonyls and other unsaturated reagents as reactants. This is one of the most elegant methods for the construction of polycyclic aromatic compounds and heteroaromatic, which have important academic and industrial uses. The thesis is divided into ten chapters including six related publications. The first study based on the Wilkinson’s catalyst, RhCl(PPh3)3, compares the reaction mechanism of the [2+2+2] cycloaddition process of acetylene with the cycloaddition obtained for the model of the complex, RhCl(PH3)3. In an attempt to reduce computational costs in DFT studies, this research project aimed to substitute PPh3 ligands for PH3, despite the electronic and steric effects produced by PPh3 ligands being significantly different to those created by PH3 ones. In this first study, detailed theoretical calculations were performed to determine the reaction mechanism of the two complexes. Despite some differences being detected, it was found that modelling PPh3 by PH3 in the catalyst helps to reduce the computational cost significantly while at the same time providing qualitatively acceptable results. Taking into account the results obtained in this earlier study, the model of the Wilkinson’s catalyst, RhCl(PH3)3, was applied to study different [2+2+2] cycloaddition reactions with unsaturated systems conducted in the laboratory. Our research group found that in the case of totally closed systems, specifically 15- and 25-membered azamacrocycles can afford benzenic compounds, except in the case of 20-membered azamacrocycle (20-MAA) which was inactive with the Wilkinson’s catalyst. In this study, theoretical calculations allowed to determine the origin of the different reactivity of the 20-MAA, where it was found that the activation barrier of the oxidative addition of two alkynes is higher than those obtained for the 15- and 25-membered macrocycles. This barrier was attributed primarily to the interaction energy, which corresponds to the energy that is released when the two deformed reagents interact in the transition state. The main factor that helped to provide an explanation to the different reactivity observed was that the 20-MAA had a more stable and delocalized HOMO orbital in the oxidative addition step. Moreover, we observed that the formation of a strained ten-membered ring during the cycloaddition of 20-MAA presents significant steric hindrance. Furthermore, in Chapter 5, an electrochemical study is presented in collaboration with Prof. Anny Jutand from Paris. This work allowed studying the main steps of the catalytic cycle of the [2+2+2] cycloaddition reaction between diynes with a monoalkyne. First kinetic data were obtained of the [2+2+2] cycloaddition process catalyzed by the Wilkinson’s catalyst, where it was observed that the rate-determining step of the reaction can change depending on the structure of the starting reagents. In the case of the [2+2+2] cycloaddition reaction involving two alkynes and one alkene in the same molecule (enediynes), it is well known that the oxidative coupling may occur between two alkynes giving the corresponding metallacyclopentadiene, or between one alkyne and the alkene affording the metallacyclopentene complex. Wilkinson’s model was used in DFT calculations to analyze the different factors that may influence in the reaction mechanism. Here it was observed that the cyclic enediynes always prefer the oxidative coupling between two alkynes moieties, while the acyclic cases have different preferences depending on the linker and the substituents used in the alkynes. Moreover, the Wilkinson’s model was used to explain the experimental results achieved in Chapter 7 where the [2+2+2] cycloaddition reaction of enediynes is studied varying the position of the double bond in the starting reagent. It was observed that enediynes type yne-ene-yne preferred the standard [2+2+2] cycloaddition reaction, while enediynes type yne-yne-ene suffered β-hydride elimination followed a reductive elimination of Wilkinson’s catalyst giving cyclohexadiene compounds, which are isomers from those that would be obtained through standard [2+2+2] cycloaddition reactions. Finally, the last chapter of this thesis is based on the use of DFT calculations to determine the reaction mechanism when the macrocycles are treated with transition metals that are inactive to the [2+2+2] cycloaddition reaction, but which are thermally active leading to new polycyclic compounds. Thus, a domino process was described combining an ene reaction and a Diels-Alder cycloaddition.

Isomerism and C-H, C-C, O-O, C-O bond activation studies by transition metals

Aquesta tesi és el reflex que de la cooperació entre grups experimentals i grups teòrics s'aconsegueix l'assoliment d'objectius inassolibles de forma individual. A partir de la DFT s'expliquen processos inorgànics i organometàl·lics de gran valor biològic i/o industrial. La tesi està enfocada especialment a l'estudi de complexos mononuclears i binuclears de coure, on té lloc l'activació d'enllaços C-H, C-C, i O-O. L'estudi de complexos octaèdrics de ruteni ha permès dur a terme extensos estudis isomèrics i racionalitzar les propietats espectroscòpiques dels mateixos. A més a més, estudis més puntuals respecte clusters de coure, l'estudi de la reacció de Pawson-Khand, l'estudi d'enllaços Pt-Pt en complexos trimèrics de platí, a més a més de l'estudi de la isomeria de complexos de Ni i Pt.