No description available.

No description available.

No description available.

No description available.

No description available.

No description available.

No description available.

No description available.

Argentina cuenta con una gran extensión de ambientes áridos y semiáridos, muchos bajo riego y con marcados problemas de desertificación, siendo fundamental la incorporación de materia orgánica para restaurar o mejorar las propiedades químicas, físicas y biológicas de los suelos. En estas mismas regiones coexisten agroindustrias que producen una gran cantidad de residuos que no son correctamente manejados, constituyendo fuentes de contaminación y que podrían ser reciclados dentro del proceso productivo en forma directa o tratados, tanto aeróbica (compostaje) como anaeróbicamente (biometanización). En esta tesis se complementaron determinaciones químicas básicas con espectroscopia UV-Visible e IR para mejorar la caracterización de los materiales e inferir su biodegradabilidad, se evaluó el efecto de la aplicación de materiales sin procesar y tratados, sobre el sistema suelo-planta utilizando la lechuga como cultivo indicador de fitotoxicidad y fertilidad. Se evaluó la activación de la microbiota y la dinámica de C a corto plazo, el efecto sobre las dinámicas de C, N y P y las comunidades procariotas en el mediano plazo bajo condiciones controladas y el efecto sobre las sustancias húmicas. Sin tratamientos fisicoquímicos previos complejos, y de forma rápida y económica, fue posible hacer una evaluación cualitativa de los componentes de los efluentes a través de sus grupos funcionales y de las interacciones entre solubilidad, peso molecular y complejidad estructural, por medio de ambos métodos espectroscópicos. Los residuos sin procesar presentaron una gran diversidad en el contenido y composición de la materia orgánica. Tanto la digestión anaeróbica como el compostaje generaron productos con mayor uniformidad que los materiales sin procesar y cada tratamiento le confirió características particulares a cada producto (digerido o compost). Los digeridos anaeróbicos presentaron una gran proporción de N inorgánico, y una alta relación N/P, mientras que los compost presentaron la situación inversa. Adicionalmente el incremento en los niveles de Ni producido por los digeridos se limita al aportado como N-NH4+ y no a su posterior mineralización, en contraposición a los compost donde el mayor aporte es por mineralización. Digeridos y compost podrían utilizarse en forma combinada para mejorar la sincronización entre la disponibilidad de nutrientes y la demanda de los cultivos. Adicionalmente, los digeridos contienen una fracción de C muy lábil compuesta principalmente por ácidos orgánicos de cadena corta y una fracción de C recalcitrante conformada por el material lignificado no degradado y polifenoles condensados. Al ser aplicado al suelo genera una rápida activación de la microbiota seguida de una rápida estabilización, generando inmovilización de C, sin modificar la abundancia de las comunidades procariotas. El aporte de N inicial estimuló a las bacterias oxidadoras del amoniaco, quienes presentaron mayor respuesta a la aplicación de los tratamientos. El digerido de cerdo incrementó el rendimiento vegetal de manera similar a los fertilizantes químicos. El biochar y el digerido de cerdo presentaron una gran complementariedad, el primero como fuente de C estable y el segundo como fuente de N y otros nutrientes disponibles. La aplicación combinada adelantó la estabilización del biochar, incrementó la disponibilidad promedio de N y la relación P lábil/ P no lábil. / Argentina has a wide range of arid and semi-arid environments, many of them under irrigation and with desertification problems. The incorporation of organic matter to restore or improve the chemical, physical and biological soil properties is crucial in those areas. Intensive agroindustrial systems (dairy farms, feed lot, pig breeding and food processing plants) coexist in these regions, providing large quantity of organic wastes that are not properly managed and constitute a source of pollution. Recycling within the productive systems, either directly or after treatment, is a more sustainable option. This thesis complemented basic chemical determinations with IR and UV-Vis spectroscopy to improve the characterization of materials and infer their biodegradability, assessed the effect of the application of raw materials and processed on the Soil-Plant system using lettuce as a crop indicator of fitotoxicity and fertility. The microbial activities and C dynamics in the short term, the effect on the dynamics of C, N, P and prokaryotes communities in the medium term under controlled conditions and the effect on humic substances were assessed. It is possible to easily make a qualitative evaluation of the effluent components through their functional groups and the interactions between solubility, molecular weight and structural complexity, by means of both spectroscopic methods, rapidly and without previous complex physicochemical treatments. The wastes without process present a complex and variable composition. Both, anaerobic digestion and aerobic processing (composting) generated products with greater uniformity than raw materials, and each treatment gave particular characteristics to the resulting product (digestate or compost). The anaerobic digestate showed a large proportion of inorganic N, and a high N/P ratio, while the compost presented the reverse situation. Additionally, the increase in the levels of inorganic N produced by the digestates is limited to the contribution as NH4+-N and not to its subsequent mineralization, as opposed to the compost, where the greatest contribution is by mineralization. Digestates and compost could be used in a combined way to improve the synchronization between nutrient availability and crop demand. Additionally, the digestates contain a fraction of very labile C, composed mainly of short-chain organic acids and a fraction of recalcitrant C, composed by the non degraded lignified material and condensed polyphenols. When applied to the soil they generate a rapid microbiota activation followed by a rapid stabilization, resulting in immobilization of C, although prokaryotes communities’ abundance remains unchanged. The N initial contribution stimulates the ammonia oxidizing bacteria, which presented a greater response to the treatments application. Pig digestate increased plant yield in a similar way to chemical fertilizers. Biochar and pig digestate presented good complementarity, the first as a source of stable C and the second as a source of N and other available nutrients. The combined application improves the stabilization of biochar, increased the N availability and the P labile/P recalcitrant ratio.

The following work describes the instrumentation and application of hyphenated FT-IR techniques specifically involving supercritical fluid extraction (SFE), supercritical fluid chromatography (SFC), and liquid chromatography (LC). Three studies are presented. The first involves the application of SFE/FT-IR towards the extraction of finishes from textile fibers. SFE has previously been applied to less complex finish systems. The proposed method making use of intermediate trapping is viable for more complex systems that show limited solubility in a supercritical fluid. Quantification of the percent finish on yarn was performed and results were favorable when compared with plant data. The range of applications was expanded to on-line SFE/SFC in the extraction and analysis of components from the polymer matrix itself. SFE/SFC/FT-IR was used to identify extractable components from a variety of Nylons. Following identification of one of the primary extractables, caprolactam, SFE/SFC was used to quantitate the amount of residual starting material in a Nylon copolymer. The second study involves the extractables in polystyrene which is a softer polymer with respect to solubility of components in supercritical CO ₂. Dimers and trimers as well as processing agents were identified via FT-IR with relatively mild supercritical extraction conditions. Following these two studies was the expansion of hyphenated FT -IR to mobile phase elimination. A system optimization was carried out using polymer additive standards. The effects of nebulizer flow, sheath flow, and sheath temperature were shown. The data were analyzed at in terms of library matches as well as GramSchmidt reconstruction peak heights. Peak intensities were the primary source for choosing optimum conditions. Under optimized conditions, approximately 200 ng of analyte were analyzed and found to be above the limit of detection. The applicability of the interface was demonstrated by the identification/analysis of triclosan, an antibacterial agent, in Colgate toothpaste. Aside from the identification of the analyte this study was used to show the effect of deposition parameters such as disk rotation rate as well as the effectiveness of FT-IR spectral library searches. The analysis of triglycerides was also carried out to show the effectiveness of using LC/FTIR for viscous liquids which are difficult analytes to deposit onto a solid substrate. Using this FT-IR technique allowed one to look at the degree of saturation/unsaturation in an olive oil sample. The linearity of the method was shown using a set of triglyceride standards. Lastly, the feasibility of using the commercially manufactured mobile phase elimination interface for SFC was demonstrated. Additive standard was deposited using both pure and methanol modified CO₂. No effluent split mechanism was used for decompressed flows up to 150 mL/min. Detection limits are proposed to fall in the low (10 - 25) ng range. The infrared spectra are enhanced over those acquired with a flow cell interface because CO₂ absorbance bands no longer obscure a portion of the analyte absorption spectrum. / Ph. D.