Rozprawy doktorskie na temat „Soil Inorganic Carbon”

Increases in atmospheric C have resulted in concerns about global warming and interest in finding means to sequester atmospheric C through land management strategies. The purpose of this study was to (i) compare changes in mineral soil C after a 30-year interval and (ii) examine the role of inorganic-N, soil texture, and topography in these changes. Soil samples were collected at permanently identified points on the Camp Branch Watershed, a second growth oak forest on the Cumberland Plateau in central Tennessee, in July of 1976 and archived. These points were re-sampled in July of 2006 and both archived and new samples of the 0 to 10 cm increment of the mineral soil were analyzed for C and N using the same procedures. Paired comparisons revealed changes in C and N were distinct to each of the 8 soil series. Comparison of 2006 samples to 1976 samples indicated changes in C concentration ranged from -13.1% to +12.0%. Changes in C mass ranged from -11.3% to +8.3%. Increases in C were most closely associated with increases in the C/total-N ratio. C was positively correlated to exchangeable inorganic-N in 1976 (r2 = 0.387) and 2006 (r2 = 0.107). Regression analysis revealed C increased with increasing azimuth and decreasing elevation in 1976 (r2 = 0.140). C was predicted only by clay content in 2006 (r2 = 0.079) and exhibited a negative relationship. Since topography was no longer a predictor of mineral soil C in 2006, we speculate that changes in forest cover also influenced changes in mineral soil C.
Master of Science

Diffuse reflectance spectroscopy (DRS) is a rapid proximal-sensing method that is being used more and more in laboratory settings to measure soil properties. Diffuse reflectance spectroscopy research that has been completed in laboratories shows promising results, but very little has been reported on how DRS will work in a field setting on soils scanned in situ. Seventy-two soil cores were obtained from six fields in Erath and Comanche County, Texas. Each soil core was scanned with a visible near-infrared (VNIR) spectrometer with a spectral range of 350-2500 nm in four different combinations of moisture content and pre-treatment: field-moist in situ, air-dried in situ, field-moist smeared in situ, and air-dried ground. Water potential was measured for the field-moist in situ scans. The VNIR spectra were used to predict total and fine clay content, water potential, organic C, and inorganic C of the soil using partial least squares (PLS) regression. The PLS model was validated with data 30% of the original soil cores that were randomly selected and not used in the calibration model. The root mean squared deviation (RMSD) of the air-dry ground samples were within the in situ RMSD and comparable to literature values for each soil property. The validation data set had a total clay content root mean squared deviation (RMSD) of 61 g kg-1 and 41 g kg-1 for the field-moist and air-dried in situ cores, respectively. The organic C validation data set had a RMSD of 5.8 g kg-1 and 4.6 g kg-1 for the field-moist and air-dried in situ cores, respectively. The RMSD values for inorganic C were 10.1 g kg-1 and 8.3 g kg-1 for the field moist and air-dried in situ scans, respectively. Smearing the samples increased the uncertainty of the predictions for clay content, organic C, and inorganic C. Water potential did not improve model predictions, nor did it correlate with the VNIR spectra; r2-values were below 0.31. These results show that DRS is an acceptable technique to measure selected soil properties in-situ at varying water contents and from different parent materials.

Thesis (MSc)--Stellenbosch University, 2015.
ENGLISH ABSTRACT: Inorganic fertilizer applications are common practice in commercial agriculture, yet not much is known regarding their interaction with organic matter and soil biota. Much research has been done on the effect of inorganic N on forest litter decomposition, yet very little research has focused on the effect of inorganic fertilizers on crop litters and, to our knowledge, none on composted organic matter. Furthermore none of the research has been done in South Africa. The main aim of this research project was to determine the effect of inorganic fertilizer applications on the decomposition of selected organic matter sources commonly used in South African agriculture and forestry. Two decomposition studies were conducted over a 3-month period, one on composts and the other on plant litters, using a local, sandy soil. In the first experiment a lower quality compost, compost A (C:N ratio, 17.67), and higher quality compost, compost B (C:N ratio, 4.92) was treated with three commercially used fertilizer treatments. Two were typical blends used for vegetable (tomato and cabbage) production: tomato fertilizer (10:2:15) (100 kg N, 20 kg P, 150 kg K per ha) and cabbage fertilizer (5:2:4) (250 kg N, 100 kg P, 200 kg K per ha). The third fertilizer blend, an equivalent mass application of N and P applied at 150 kg of each element per ha, is more commonly used in pastures. In the second experiment, five commonly encountered crop and forestry litters, namely kikuyu grass, lucerne residues, pine needles, sugar cane trash and wheat straw, were selected to represent the labile organic matter sources. The litters were treated with the tomato and cabbage fertilizer applications rates. Both decomposition experiments were conducted under ambient laboratory conditions at field water capacity. Decomposition rates were monitored by determining CO2 emissions, DOC production, β-glucosidase and polyphenol oxidase activity (PPO). At the start and end of decomposition study, loss on ignition was performed to assess the total loss of OM. Based on the results obtained from these two experiments, it was concluded that the addition of high N containing inorganic fertilizers enhanced the decomposition of both composted and labile organic matter. For both compost and plant litters, DOC production was greatly enhanced with the addition of inorganic fertilizers regardless of the organic matter quality. The conclusion can be made that inherent N in organic matter played a role in the response of decomposition to inorganic fertilizer application with organic matter low in inherent N showing greater responses in decomposition changes. For labile organic matter polyphenol and cellulose content also played a role in the responses observed from inorganic fertilizer applications.
AFRIKAANSE OPSOMMING: Anorganiese kunsmis toedieningss is algemene praktyk in die kommersiële landbou sektor,maar nog min is bekend oor hul interaksie met organiese materiaal en grond biota. Baie navorsing is reeds oor die uitwerking van anorganiese N op woud en plantasiereste se ontbinding gedoen. Baie min navorsing het gefokus op die uitwerking van anorganiese kunsmis op die gewasreste en tot ons kennis, is daar geen navorsing gedoen op die invloed van anorganiese kunsmis op gekomposteer organiese material nie. Verder is geeneen van die navorsing studies is in Suid-Afrika gedoen nie. Die hoofdoel van hierdie navorsingsprojek was om die effek van anorganiese kunsmis toedienings op die ontbinding van geselekteerde organiese materiaal bronne, wat algemeen gebruik word in die Suid-Afrikaanse landbou en bosbou, te bepaal. Twee ontbinding studies is gedoen oor 'n 3-maande-tydperk, een op kompos en die ander op die plantreste, met die gebruik van 'n plaaslike, sanderige grond. In die eerste eksperiment is ‘n laer gehalte kompos, kompos A (C: N verhouding, 17.67), en 'n hoër gehalte kompos, kompos B (C: N verhouding, 4.92) met drie kommersieel anorganiese bemesting behandelings behandel. Twee was tipiese versnitte gebruik vir die groente (tamatie en kool) produksie: tamatie kunsmis (10: 2:15) (100 kg N, 20 kg P, 150 kg K per ha) en kool kunsmis (5: 2: 4) (250 kg N, 100 kg P, 200 kg K per ha). Die derde kunsmis versnit was 'n ekwivalente massa toepassing van N en P van 150 kg van elke element per ha, wat meer algemeen gebruik word in weiding. In die tweede eksperiment was vyf algemeen gewas en bosbou reste, naamlik kikoejoegras, lusern reste, dennenaalde, suikerriet reste en koring strooi, gekies om die labiele organiese materiaal bronne te verteenwoordig. Die reste is met die tamatie en kool kunsmis toedienings behandel. Beide ontbinding eksperimente is uitgevoer onder normale laboratorium toestande by veldwaterkapasiteit. Ontbinding tempo is deur die bepaling van die CO2-vrystellings, opgelosde organiese koolstof (OOK) produksie, β-glukosidase en polifenol oksidase aktiwiteit (PPO) gemonitor. Aan die begin en einde van ontbinding studie, is verlies op ontbranding uitgevoer om die totale verlies van OM te evalueer. Gebaseer op die resultate van hierdie twee eksperimente, was die gevolgtrekking dat die toevoeging van hoë N bevattende anorganiese bemestingstowwe die ontbinding van beide komposte en plant reste verhoog. Vir beide kompos en plantreste word OOK produksie verhoog met die toevoeging van anorganiese bemesting, ongeag van die organiese materiaal gehalte. Die gevolgtrekking kan gemaak word dat die inherente N in organiese materiaal 'n rol gespeel het in die reaksie van ontbinding op anorganiese bemesting toedienings met die grootste reaksie in organiese material laag in inherente N. Vir labiele organiese material het polifenol en sellulose inhoud ook 'n rol gespeel in die reaksie waargeneeming op anorganiese bemesting.

Soil P fractionation was used to examine changes in soil inorganic and organic P under grazed irrigated pasture in a long-term field trial at Winchmore in Mid-Canterbury. The soil P fractionation scheme used involved sequential extractions of soil with O.5M NaHCO₃ @ pH 8.5 (NaHCO₃ P), 0.1M NaOH (NaOH I P), 1M HCl (HCl P) and 0.1M NaOH (NaOH II P). The Winchmore trial comprised 5 treatments: control (no P since 1952), 376R (376 kg superphosphate ha⁻¹ yr⁻¹ 1952-1957, none since), 564R (564 kg superphosphate ha⁻¹ yr⁻¹ 1952-1957, none since) 188PA (188 kg superphosphate ha⁻¹ yr⁻¹ since 1952) and 376PA (376 kg superphosphate ha⁻¹ yr⁻¹ since 1952: Topsoil (0-7.5cm) samples taken from the different treatments in 1958, 1961, 1965, 1968, 1971, 1974 and 1977 were used in this study. Changes in soil P with time showed that significant increases in soil inorganic P occurred in the annually fertilised treatments (l88PA, 376PA). As expected, the overall increase in total soil inorganic P between 1958 and 1977 was greater in the 376PA treatment (159 µg P g⁻¹) than that in the 188PA treatment (37 µg P g⁻¹). However, the chemical forms of inorganic P which accumulated in the annually fertilised treatments changed with time. Between 1958 and 1971 most of the increases in soil inorganic P in these treatments occurred in the NaHCO₃ and NaOH I P fractions. On the other hand, increases in soil inorganic P in the annually fertilised treatments between 1971 and 1977 were found mainly in the HCl and NaOH II P fractions. These changes in soil P forms were attributed to the combined effects of lime addition in 1972 and increased amounts of sparingly soluble apatite P and iron-aluminium P in the single superphosphate applied during the 1970's. In the residual fertiliser treatments (376R, 564R) significant decreases in all of the soil inorganic P fractions (i.e. NaHCO₃ P, NaOH I P, HCl P, NaOH II p) occurred between 1958 and 1977 following the cessation of P fertiliser inputs in 1957. This was attributed to continued plant uptake of P accumulated in the soil from earlier P fertiliser additions. However, levels of inorganic P in the different soil P fractions in the residual fertiliser treatments did not decline to those in the control which indicated that some of the inorganic P accumulated in the soil from P fertiliser applied between 1952 and 1957 was present in very stable forms. In all treatments, significant increases in soil organic P occurred between 1958 and 1971. The overall increases in total soil organic P were greater in the annually fertilised treatments (70-86 µg P g⁻¹) than those in the residual fertiliser (55-64 µg P g⁻¹) and control (34 µg P g⁻¹) treatments which reflected the respective levels of pasture production in the different treatments. These increases in soil organic P were attributed to the biological conversion of native and fertiliser inorganic P to organic P in the soil via plant, animal and microbial residues. The results also showed that annual rates of soil organic P accumulation between 1958 and 1971 decreased with time which indicated that steady-state conditions with regard to net 'organic P accumulation were being reached. In the residual fertiliser treatments, soil organic P continued to increase between 1958 and 1971 while levels of soil inorganic P and pasture production declined. This indicated that organic P which accumulated in soil from P fertiliser additions was more stable and less available to plants than inorganic forms of soil P. Between 1971 and 1974 small (10-38 µg P g⁻¹) but significant decreases in total soil organic P occurred in all treatments. This was attributed to increased mineralisation of soil organic P as a result of lime (4 t ha⁻¹) applied to the trial in 1972 and also to the observed cessation of further net soil organic P accumulation after 1971. Liming also appeared to affect the chemical nature of soil organic P as shown by the large decreases in NaOH I organic P(78-88 µg P g⁻¹) and concomitant smaller increases in NaOH II organic P (53-65 µg P g⁻¹) which occurred in all treatments between 1971 and 1974. The chemical nature of soil organic P in the Winchmore long-term trial was also investigated using 31p nuclear magnetic resonance (NMR) spectroscopy and gel filtration chromatography. This involved quantitative extraction of organic P from the soil by sequential extraction with 0.1M NaOH, 0.2M aqueous acetylacetone (pH 8.3) and 0.5M NaOH following which the extracts were concentrated by ultrafiltration. Soils (0-7.5cm) taken from the control and 376PA annually fertilised treatments in 1958, 1971 and 1983 were used in this study. 31p NMR analysis showed that most (88-94%) of the organic P in the Winchmore soils was present as orthophosphate monoester P while the remainder was found as orthophosphate diester and pyrophosphate P. Orthophosphate monoester P also made up almost all of the soil organic P which accumulated in the 376PA treatment between 1958 and 1971. This indicated that soil organic P in the 376PA and control treatments was very stable. The gel filtration studies using Sephadex G-100 showed that most (61-83%) of the soil organic P in the control and 376PA treatments was present in the low molecular weight forms (<100,000 MW), although the proportion of soil organic P in high molecular weight forms (>100,000 MW) increased from 17-19% in 1958 to 38-39% in 1983. The latter was attributed to the microbial humification of organic P and indicated a shift toward more complex and possibly more stable forms of organic P in the soil with time. Assuming that the difference in soil organic P between the control and 376PA soils sampled in 1971 and 1983 represented the organic P derived from P fertiliser additions, results showed that this soil organic P was evenly distributed between the high and low molecular weight fractions. An exhaustive pot trial was used to examine the relative availability to plants of different forms of soil inorganic and organic P in long-term fertilised pasture soils. This involved growing 3 successive crops of perennial ryegrass (Lolium perenne) in 3 Lismore silt loam (Udic Ustochrept) soils which had received different amounts of P fertiliser for many years. Two of the soils were taken from the annually fertilised treatments in the Winchmore long term trial (188PA, 376PA) and the third (Fairton) was taken from a pasture which had been irrigated with meatworks effluent for over 80 years (65 kg P ha⁻¹ yr⁻¹). Each soil was subjected to 3 treatments, namely control (no nutrients added), N100 and N200. The latter treatments involved adding complete nutrient solutions with different quantities of N at rates of 100kg N ha⁻¹ (N100) and 200kg N ha⁻¹ (N200) on an area basis. The soil P fractionation scheme used was the same as that used in the Winchmore long-term trial study (i.e. NaHCO₃ P, NaOH I P, HCl P, NaOH II p). Results obtained showed that the availability to plants of different extracted inorganic P fractions, as measured by decreases in P fractions before and after 3 successive crops, followed the order: NaHCO₃ P > NaOH I P > HCl P = NaOH II P. Overall decreases in the NaHCO₃ and NaOH I inorganic P fractions were 34% and 16% respectively, while corresponding decreases in the HCl and NaOH II inorganic P fractions were small «10%) and not significant. However, a significant decrease in HCl P (16%) was observed in one soil (Fairton-N200 treatment) which was attributed to the significant decrease in soil pH (from 6.2 to 5.1) which occurred after successive cropping. Successive cropping had little or no effect on the levels of P in the different soil organic P fractions. This indicated that net soil organic P mineralisation did not contribute significantly to plant P uptake over the short-term. A short-term field experiment was also conducted to examine the effects of different soil management practices on the availability of different forms of P to plants in the long-term fertilised pasture soils. The trial was sited on selected plots of the existing annually fertilised treatments in the Winchmore long-term trial (188PA, 376PA) and comprised 5 treatments: control, 2 rates of lime (2 and 4 t ha⁻¹ ) , urea fertiliser (400kg N ha⁻¹ ) and mechanical cultivation. The above ground herbage in the uncultivated treatments was harvested on 11 occasions over a 2 year period and at each harvest topsoil (0-7.5 cm) samples were taken from all of the treatments for P analysis. The soil P fractionation scheme used in this particular trial involved sequential extractions with 0.5M NaHCO₃ @ pH 8.5 (NaHCO₃ P), 0.1M NaOH (NaOH P), ultrasonification with 0.1M NaOH (sonicate-NaOH p) and 1M HCl (HCl P). In addition, amounts of microbial P in the soils were determined. The results showed that liming resulted in small (10-21 µg P g⁻¹) though significant decreases in the NaOH soil organic P fraction in the 188PA and 376PA plots. Levels of soil microbial P were also found to be greater in the limed treatments compared with those in the controls. These results indicated that liming increased the microbial mineralisation of soil organic P in the Winchmore soils. However, pasture dry matter yields and P uptake were not significantly affected. Although urea significantly increased dry matter yields and P uptake, it did not appear to significantly affect amounts of P in the different soil P fractions. Mechanical cultivation and the subsequent fallow period (18 months) resulted in significant increases in amounts of P in the NaHCO₃ and NaOH inorganic P fractions. This was attributed to P released from the microbial decomposition of plant residues, although the absence of plants significantly reduced levels of microbial P in the cultivated soils. Practical implications of the results obtained in the present study were presented and discussed.

A mudança do uso da terra modifica os ciclos dos elementos no solo, com alterações nos fluxos dos gases do efeito estufa (GEE). O tempo de implantação do sistema plantio direto associado a uma planta de cobertura (SPD) pode recuperar o estoque de carbono (C) no solo e mitigar o aumento da temperatura global devido à elevação da concentração dos gases do efeito estufa. Assim, o objetivo deste trabalho foi avaliar as alterações nos estoques de C e N do solo com o tempo de implantação do SPD tomando como referência absoluta a condição original (Cerradão) e, também com referencia relativa áreas com mudança do uso da terra, uma sob pastagem, e outra sob plantio convencional. O estudo foi realizado em áreas situadas no município de Rio Verde-GO (17º50\' a 18º20\' S e 51º43\' a 50º19\' O), em um Latossolo Vermelho distrófico com teores de argila entre 50 e 70 %. O delineamento experimental empregado foi inteiramente casualisados com parcelas subdivididas, constando de doze áreas, estas divididas em três sub-áreas cada qual com seis pontos de amostragem e cinco profundidades (0-5, 5-10, 10-20, 20-30 e 30-40 cm). As áreas amostradas foram três sob Cerradão (CE, 2CE e 3CE); uma sob pastagem (PA), uma sob plantio convencional (PC), e sete em SPD com uma área de conversão do plantio convencional para o SPD (PD 0) e áreas com 4, 5, 7, 8, 10 e 12 anos de implantação do sistema (PD 4, PD 5, PD 7, PD 8, PD 10, PD 12). As variáveis estudadas foram: os atributos físicos e químicos, os estoques de C e N e a composição isotópica do 13C/12C e 15N/14N. Os fluxos dos GEE (CO2, N2O e CH4) foram determinados no CE, PA PC e PD com 8, 10 e 12 anos, além das quantidades de N-inorgânico e C e N-microbiano. Os resultados deste estudo mostraram que o SPD promoveu melhoria nos atributos físicos como a redução da compactação do solo, e nos atributos químicos como o aumento do pH e da disponibilidade de K, P, Ca e magnésio nas camadas superficiais do solo. Os estoques de C e N foram maiores nas áreas sob Cerradão (80 e 4 Mg ha-1, respectivamente para o C e N). Os menores valores nos estoques de C foram reportados no PD 0, PC e PA (54; 62 e 64 Mg ha-1, respectivamente). O tempo de implantação do SPD aumentou o estoque de C no solo, de modo que no PD 12 foi encontrado estoque de C igual as áreas sob Cerradão. A taxa anual de acúmulo de C no SPD foi calculada em 1,26 Mg ha-1 ano-1 (0-40 cm). As quantidades médias de C e N-microbiano e N-inorgânico foram encontradas no CE, o Nnitrato correspondeu a 60 % do total em todas as áreas. A maior emissão total em Cequivalente foi observado na PA (160 kg ha-1 ano-1), no CE foi de 135 kg ha-1 ano-1, enquanto que para o PC e SPD as emissões foram de 121 e 129 kg ha-1 ano-1, respectivamente. O seqüestro de C no solo sob SPD para a situação avaliada foi de 1,13 Mg ha-1 ano-1. O SPD mostrou neste estudo, que é uma prática agrícola que melhora as condições do solo, promovendo o aumento no estoque de C sem o aumento nas emissões de N2O e CH4 podendo tornar-se uma alternativa para mitigar as emissões dos GEE, garantindo a sustentabilidade do sistema produtivo
The land-use change transforms the elements cycles in the soil, with alterations in the greenhouse gas (GHG) emissions. The time of implementation of the no-tillage system associated with a cover crop (NT) can recover the carbon (C) stocks in the soil and thus mitigate the global temperature increase due increasing GHG concentration. Therefore, the objective of this work was to evaluate the alterations of the soil carbon and nitrogen stocks following implementation time of no-tillage (NT) system taking as absolute reference the original condition (Cerradão) and, also, as relative reference, areas with other land use change, one under pasture, and other under conventional tillage. The study was done in areas located at Rio Verde (Goias state, Brazil) (17°50\' to 18°20\' S and 51°43\' to 50°19\' W), in a Oxisol (very clayed Red Dystrofic typic Latosol) with clay contents in the range 50 - 70 %. At each site, samples were taken randomly with subdivided parcels; these sites were divided in three sub-areas with six sampling locations and five depths (0-5, 5-10, 10-20, 20-30, 30-40 cm.). The sampled sites were three under ?Cerradão? (CE, 2CE and 3CE); one pasture (PA), one conventional tillage (CT), and seven situations under no-tillage system with an area recently converted from conventional tillage to no-tillage (NT 0), and areas with 4, 5, 7, 8, 10 and 12 years of implementation of the no-tillage (NT-4, NT-5, NT-7, NT-8, NT-10 and NT- 12). The variables studied were: physical and chemical attributes, the C and N stocks and the isotopic composition of 13C/12C and 15N/14N. The GHG emissions (CO2, N2O and CH4) were measured in CE, PA, CT and NT with 8, 10, and 12 years together with the quantity of inorganic-N and microbial C and N. The results of this study showed that these no-tillage systems guaranteed the physical attribute improvement with the decrease of the soil compaction and in the chemical attributes with increase of pH and of the availability of K, P, Ca and magnesium in the soil superficial layers. The carbon and nitrogen stocks were higher in ?Cerradão? (80 and 4 Mg ha-1, respectively to C and N). The lowest values in the carbon stocks were reported in NT-0, CT and PA (54; 62 and 64 Mg ha-1, respectively). The implementation time of no-tillage (NT) system increased the carbon stock in the soil, leading to carbon stock in the NT-12 area in the same level of the ?Cerradão? areas. The annual soil C accumulation in the NT system was calculated in 1,26 Mg ha-1 yr?1 (0-30 cm). For all areas, the average quantities of C and microbial-N and inorganic-N were found in CE, nitrate-N corresponded 60 % of the total. The highest total emission in C-equivalent was observed in PA (160 kg ha-1 yr-1), in CE it was 135 kg ha-1 yr-1, and amounted 121 and 129 135 kg ha-1 yr-1 for the CT and NT respectively. The carbon sequestration in the soil under (NT) for the studied situations was 1,13 Mg ha-1 yr-1. The No-tillage (NT) system studied showed to be an agricultural practice that improves the soil condition, promoting the increase of carbon stock without the increase of N2O and CH4 emissions, being thus an alternative to diminish the GHG emissions, and guaranteeing the sustainability of the productive system

Syftet med examensarbetet har varit att studera kol i mindre vattendrag med hjälp av jämviktsmodellering i PHREEQC. Fokus har varit dynamik av löst icke organiskt kol (DIC) samt att förstå hur mycket koldioxid (CO2) som avges från mindre vattendrag och om den mängden har signifikant inverkan på den globala kolbalansen. Med hjälp av provtagen data från Krycklans avrinningsområde år 2003-2007 och 2009 har modellering av DIC och pCO2 utförts med målet att se förändring både över säsong och nedströms i ytvattensystemet. För att utvärdera modellen har tillhandahållen data över uppmätt pCO2 använts. Målet var att jämföra modellerade och tillhandahållna pCO2-värden för att se hur väl modellen kunde beskriva verkligheten och om den fungerade bättre för någon plats eller under vissa delar av året. Analysen visade att pCO2-värden för modellen följer uppmätta pCO2-värden förhållandevis bra. Avvikelserna var störst för en av provpunkterna (provpunkt 6). Modellerade pCO2-värden följde de uppmätta pCO2-värden bäst under vårfloden. Modellen och analys av data visade tydliga indikationer på en avgång av CO2 från vattendraget.
The purpose of this Master thesis has been to study carbon flux in creeks. Chemical equilibrium models were produced to this end using PHREEQC. Specifically, dissolved inorganic carbon (DIC) quantities have been studied in order to understand the discharge of carbon dioxide (CO2) from the creek headwaters and how that affects the global carbon balance. Modeling of DIC and pCO2 was conducted using data from 2003-2007 and 2009 sampled at two points in the Krycklan research catchment located in northern Sweden. Seasonal variation of DIC and pCO2 in the two sample points was studied as well as the difference of these quantities between the two points. Evaluation of the model was done in part by comparing predicted pCO2 values with actual values stemming from a previous study leading to an assessment of the validity of the model. One of the sample points showed larger discrepancies between predictedand actual values than the other. Studying the seasonal variation of discrepancies, they were at the minimum during the spring flood. Finally, the analysis showed clear indications of a net CO2 discharge from the creekstretch between the two sample points.

Novel highly functionalized hybrid organic-inorganic materials were synthesized by polycondensation of bis[3-(trimethoxysilyl)propyl]amine in presence of cationic and anionic surfactants. Reaction media strongly affected gelation time. Thus, in basic media gelation occurred immediately while acid increased gelation time. Material structures were studied by IR spectroscopy, porosimetry, XRD, and SAXS methods. In spite of the absence of an inorganic linker, obtained bridged silsesquioxanes had mesoporous structure. A material prepared in the presence of dodecylamine as a template had higher surface area and narrow pore size distribution while the use of sodium dodecylbenzene sulfate resulted in formation of mesopores with wide size ranges. Accessibility of surface amine groups in silsesquioxanes was studied for molecules of acidic nature and different sizes: HCl, CO2 and picric acid. High contents of accessible amine groups in these materials make them prospective adsorbents for post-combustion CO2 capture.

Made available in DSpace on 2016-12-08T17:19:34Z (GMT). No. of bitstreams: 1 01_Capa_Sumario.pdf: 97224 bytes, checksum: 84cdd855f48b9820d3374a610091b98c (MD5) Previous issue date: 2010-02-19
Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
The main goal of this work was the synthesis of silsesquioxane oligomers containing amine and phenyl groups, and the subsequent formation of an organic-inorganic hybrid by reaction of amine groups of the silsesquioxane precursor with the epoxy rings of bisphenol A diglycidyl ether (BADGE). The sol-gel process adopted in the oligomers syntheses proved to be efficient for the condensation reaction between 3-aminopropyltriethoxysilane and phenyltriethoxysilane. Epoxy-silsesquioxane hybrids prepared from oligomers with different condensation degrees were studied. These matrices were further reinforced with 0.25 % (w/w) of multi-walled carbon nanotube (MWCNT). Resin transfer molding (RTM) was also used to produce reinforced nanocomposites with carbon fiber (CF) and MWCNT (0.25 and 0,50 % (w/w)). Liquid state 29Si nuclear magnetic resonance analysis indicated that T3 structure is the major phase forming the synthesized oligomer. Infrared spectroscopy analyses confirmed the formation of epoxy-copolysilsesquioxane hybrid and showed that a high degree of cure was achieved after the addition of an aliphatic polyamine, however, an increase in thermal stability of produced hybrids was not observed. Glass transition temperatures (Tg) obtained by dilatometry and DMA did not show a trend of increase or decrease in this property for the produced hybrids by casting. The cured hybrids presented a brittle type fracture, similar to epoxy resin. The addition of MWCNT to the hybrid matrix did not influence the tensile mechanical properties (Young modulus and tensile strength) and caused a reduction in the Tg of the nanocomposites. Good wettability of CF by resin was observed in the nanocomposites obtained by RTM, providing significant increases in mechanical properties under tensile and impact, however, the Tg s decreased by 30 % in relation to epoxy. Unlike casting molding, the addition of MWCNT in the RTM process provided a significant increase in the mechanical properties analyzed.
Este trabalho teve por objetivo a síntese de oligômeros de silsesquioxanos contendo grupos amino e fenil, e a posterior formação de um híbrido orgânico-inorgânico pela reação dos grupos amino do precursor silsesquioxano com o anel epoxídico da resina diglicidil éter de bisfenol A (DGEBA). O processo sol-gel adotado na síntese dos oligômeros demonstrou ser eficiente na reação de condensação entre o 3-aminopropiltrietoxissilano e feniltrietoxissilano. Matrizes híbridas com silsesquioxanos de diferentes graus de condensação foram estudadas. A estas matrizes foram adicionados 0,25 % (m/m) de nanotubos de carbono de paredes múltiplas (MWCNT). A moldagem por transferência de resina (RTM) foi utilizada na produção de nanocompósitos reforçados com fibra de carbono (CF) e MWCNT (0,25 e 0,50 % (m/m)). Análise de ressonância magnética nuclear 29Si em solução revelou que o sítio T3 é a maior fase constituinte do oligômero sintetizado. Espectroscopia de infravermelho confirmou a formação do híbrido epóxidocopolissilsesquioxano e mostrou que um alto grau de cura foi atingido após a adição de uma poliamina alifática, contudo, não se observou aumento na estabilidade térmica dos híbridos produzidos. As temperaturas de transição vítrea (Tg) obtidas por dilatometria e DMA não apresentaram uma tendência de aumento ou decréscimo nesta propriedade dos híbridos produzidos por casting. Os híbridos curados apresentaram caráter de fratura do tipo frágil, semelhante à resina epoxídica. A adição de MWCNT às matrizes híbridas não influenciou as propriedades mecânicas sob tração (módulo de elasticidade e tensão máxima) e provocou uma diminuição da Tg nos respectivos nanocompósitos. Uma boa molhabilidade das CF pela resina foi observada nos nanocompósitos obtidos por RTM proporcionando aumentos expressivos nas propriedades mecânicas sob tração e impacto, contudo, as Tg s apresentaram uma queda de 30 % em relação ao epóxido. Ao contrário da moldagem por casting, no RTM a adição de MWCNT proporcionou aumentos significativos nas propriedades mecânicas analisadas.

La multiplication des microboutures au cours des subcultures est caractérisée par une évolution de l'état physiologique qui dépend de l’âge, des réserves nutritives et du milieu de culture. Parmi les problèmes qui limitent la multiplication végétative: l'hyperhydrie et le gonflement des tiges des microboutures. Le premier est caractérisé par une teneur en eau élevée, par des rapports p/na, k/na et cytokinines/auxine élevés. Le deuxième est caractérisé par une teneur élevé en zéatine+zéatine-riboside. Les méristèmes de plantes d'âges différents ont une réactivité distincte aux niveaux morphologique et physiologique.

The International Energy Agency estimated that lighting accounts for ~19% of the total worldwide energy consumption. Light emitting diodes (LEDs) have higher efficiency compared to that of conventional lighting sources. The commercial white-LEDs (WLEDs) are based on broad-band Y3Al5O12:Ce3+ (YAG:Ce) yellow phosphor in combination with blue LED chips through a low cost and simple procedure, in which the YAG:Ce phosphor is directly packed on the blue InGaN chip. However, such two colour-based WLEDs exhibit poor colour rendering index (CRI, usually <75), high correlated colour temperature (CCT, >6500 K), and chromaticity drifts, which cannot fully satisfy the applications of lighting and backlighting of the displays. Also, LEDs still face some other drawbacks such as the relatively low efficient green emission, termed the ³green gap´ issXe. A promising alternative strategy is based on the downshift of the electroluminescence of near ultra-violet (NUV)/blue LEDs into the green spectral region by UV/blue-down shifting phosphors. Thus, novel efficient white and green-emitting materials for the phosphor-converted LED applications are required. In this thesis, organic-inorganic hybrids (ureasils, d-U(600)) doped with green emitting Tb3+-based complexes were applied in combination with NUV-LED chips to fabricate efficient green LED prototypes. To improve CRI and CCT of commercial WLEDs, novel blue-light excited La2Ce2O7:Eu3+ red phosphors were also successfully synthesised and characterized. Moreover, tuned white light emitters involving d-U(600) hybrids doped with lanthanide (Ln3+=Tb3+, Eu3+)-based complexes, fluorescent dyes (e.g. coumarin), and carbon dots were also prepared and optically characterised revealing intriguing CCT, CRI and photostability towards novel WLEDs.
A Agência Internacional de Energia estimou que o sector de iluminação representa cerca de 19% do consumo total de energia mundial. Os díodos emissores de luz (LEDs) têm maior eficiência em comparação com as fontes de iluminação convencionais. Os LEDs brancos comerciais (WLEDs) são baseados na combinação de LEDs azuis baseados em InGaN com o luminóforo Y3Al5O12:Ce3+ (YAG:Ce). Este material, que é um emissor de banda larga na região espectral do amarelo. é depositado de forma simples e a baixo custo sobre o LED azul. No entanto, a emissão deste WLEDs baseia-se na adição de duas cores tendo um índice de reprodução de cor baixo (CRI, geralmente <75), elevada temperatura de cor (CCT, > 6500 K) e variação de cromaticidade, que são claras desvantagens em aplicações de iluminação e retroiluminação. Para além destas desvantagens, estes LEDs ainda apresentam emissão na região do verde relativamente menos eficiente (usualmente designado em linguagem inglesa como ³green gap issue´). Uma estratégia alternativa a estes LEDs baseia-se na utilização de dispositivos emissores nas regiões espectrais do ultravioleta próximo (NUV) e do azul combinados com um material capaz de desviar esta emissão para a região do visível. Assim, novos materiais emissores eficientes quer de luz verde quer de luz branca para as aplicações em LEDs são necessários. Nesta tese, híbridos orgânicos-inorgânicos (ureasils, d-U(600)) dopados com complexos à base de Tb3+ emissores no verde foram combinados com NUV-LED comerciais para fabricar protótipos de LED verdes eficientes. Para melhorar o CRI e CCT dos WLEDs comerciais, novos luminóforos de La2Ce2O7:Eu3+ com emissão no vermelho e excitados com LEDs azuis foram, também, sintetizados e caracterizados. Na parte final da tese discute-se a contribuição de novos materiais emissores de luz branca sintonizável baseados em híbridos d-U(600) dopados com complexos de iões lantanídeos (Ln3+=Tb3+, Eu3+), corantes fluorescentes e pontos de carbono com propriedades óticas (CCT, CRI e fotoestabilidade) melhoradas, face ao estado da arte.
Programa Doutoral em Ciência e Engenharia de Materiais

Cereal rye (CR), the most common and effective nitrogen (N) scavenging cover crop option in the Midwest, is often utilized in cropping systems to reduce nitrate loss for environmental benefits. To increase environmental efficiency in Midwest corn cropping systems, we must increase the overall adoption of CR. However, due to the yield reduction potential (6%) for corn planted after CR termination, CR is primarily recommended before soybean. To increase CR adoption, we must develop adaptive fertilizer management practices that achieve competitive grain yields relative to cropping systems where CR is not adopted. Therefore, the objectives of this study are to determine (1) the effect of CR and starter nitrogen rate on corn growth and nitrogen content. (2) the optimum starter nitrogen rate to achieve agronomic optimum corn yield following CR. (3) the impact of phosphorus (P) at starter on plant growth, nitrogen content, and yield with the inclusion of CR. For our study, five starter N rates were applied in a 5x5 cm band to both CR and non-CR plots, concentrations ranged from 0-84 kg N ha^-1 in 28 kg N ha^-1 intervals. Total N applied was the same for each treatment, relative to its location, and was split between starter N at planting and sidedress applied at growth stage V6 relatively. Although CR termination took place at least two weeks before planting, CR decreased corn grain yield at one of three locations by an average of 8%, nitrogen recovery efficiency (NRE) by 27%, and R6 total N content by 23%, relative to the conventional control (non-CR 0N), when no starter N was applied. At one of three locations, starter N rates of 56 kg N ha^-1, 56 kg N ha^-1 plus 17 kg P ha^-1, and 84 kg N ha^-1 increased corn grain yield, in CR plots, and 56 kg N ha^-1 plus 17 kg P ha^-1 increased corn grain yield in non-CR plots. Phosphorus increased corn grain N content at growth stage R6 in one of three locations and did not impact corn grain yield at all locations. We conclude that the inclusion of starter N at planting has the potential to increase agronomic productivity in CR corn cropping systems in soil environments with a high capacity to mineralize soil N. However, further research is required to refine our starter N results to find an optimum starter N rate to apply before planting corn following CR.