Improved Dynamic Headspace Sampling and Detection using Capillary Microextraction of Volatiles Coupled to Gas Chromatography Mass Spectrometry

Sampling and preconcentration techniques play a critical role in headspace analysis in analytical chemistry. My dissertation presents a novel sampling design, capillary microextraction of volatiles (CMV), that improves the preconcentration of volatiles and semivolatiles in a headspace with high throughput, near quantitative analysis, high recovery and unambiguous identification of compounds when coupled to mass spectrometry. The CMV devices use sol-gel polydimethylsiloxane (PDMS) coated microglass fibers as the sampling/preconcentration sorbent when these fibers are stacked into open-ended capillary tubes. The design allows for dynamic headspace sampling by connecting the device to a hand-held vacuum pump. The inexpensive device can be fitted into a thermal desorption probe for thermal desorption of the extracted volatile compounds into a gas chromatography-mass spectrometer (GC-MS). The performance of the CMV devices was compared with two other existing preconcentration techniques, solid phase microextraction (SPME) and planar solid phase microextraction (PSPME). Compared to SPME fibers, the CMV devices have an improved surface area and phase volume of 5000 times and 80 times, respectively. One (1) minute dynamic CMV air sampling resulted in similar performance as a 30 min static extraction using a SPME fiber. The PSPME devices have been fashioned to easily interface with ion mobility spectrometers (IMS) for explosives or drugs detection. The CMV devices are shown to offer dynamic sampling and can now be coupled to COTS GC-MS instruments. Several compound classes representing explosives have been analyzed with minimum breakthrough even after a 60 min. sampling time. The extracted volatile compounds were retained in the CMV devices when preserved in aluminum foils after sampling. Finally, the CMV sampling device were used for several different headspace profiling applications which involved sampling a shipping facility, six illicit drugs, seven military explosives and eighteen different bacteria strains. Successful detection of the target analytes at ng levels of the target signature volatile compounds in these applications suggests that the CMV devices can provide high throughput qualitative and quantitative analysis with high recovery and unambiguous identification of analytes.

Co-Composting of Poultry Manure with Different Organic Amendments

To study the influence of different organic amendments on the quality of poultry manure compost, three pilot composting trials were carried out with different mixes: poultrymanure/carcasse meal/ashes/grape pomace (Pile 1), poultry manure/cellulosic sludge (Pile 2) and poultry manure (Pile 3). For all piles, wood chips were applied as bulking agent. The process was monitored, over time, by evaluating standard physical and chemical parameters, such as, pH, electric conductivity, moisture, organic matter and ash content, total carbon and total nitrogen content, carbon/nitrogen ratio (C/N) and content in mineral elements. Piles 1 and 2 reached a thermophilic phase, however having different trends. Pile 1 reached this phase earlier than Pile 2. For both, the pH showed a slight alkaline character and the electric conductivity was lower than 2 mS/cm. Also, the initial C/N value was 22 and reached values lower than 15 at the end of composting process. The total N content of the Pile 1 increased slightly during composting, in contrast with the others piles. At the end of composting process, the phosphorus content ranged between 54 and 236 mg/kg dry matter, for Pile 2 and 3, respectively. Generally, the Piles 1 and 3 exhibited similar heavy metals content. This study showed that organic amendments can be used as carbon source, given that the final composts presented parameters within the range of those recommended in the 2nd Draft of EU regulation proposal (DG Env.A.2 2001) for compost quality.

Characterization of MSW rejected fractions to fulfill RDF requirements and utilization

In order to fulfil European and Portuguese legal requirements, adequate alternatives to traditional municipal waste landfilling must be found namely concerning organic wastes and others susceptible of valorisation. According to the Portuguese Standard NP 4486:2008, refuse derived fuels (RDF) classification is based on three main parameters: lower heating value (considered as an economic parameter), chlorine content (considered as a technical parameter) and mercury content (considered as an environmental parameter). The purpose of this study was to characterize the rejected streams resulting from the mechanical treatment of unsorted municipal solid waste, from the plastic municipal selective collection and from the composting process, in order to evaluate their potential as RDF. To accomplish this purpose six sampling campaigns were performed. Chemical characterization comprised the proximate analysis – moisture content, volatile matter, ashes and fixed carbon, as well as trace elements. Physical characterization was also done. To evaluate their potential as RDF, the following parameters established in the Portuguese standard were also evaluated: heating value and chlorine content. As expected, results show that the refused stream from mechanical treatment is rather different from the selective collection rejected stream and from the rejected from the compost screening in terms of moisture, energetic matter and ashes, as well as heating value and chlorine. Preliminary data allows us to conclude that studied materials have a very interesting potential to be used as RDF. In fact, the rejected from selective collection and the one from composting have a heating value not very different from coal. Therefore, an important key factor may be the blending of these materials with others of higher heating values, after pre-processing, in order to get fuel pellets with good consistency, storage and handling characteristics and, therefore, combustion behavior.

Carbon in humic fractions of organic matter in soil treated with organic composts under mango cultivation.

Soil organic matter (SOM) plays a key role in maintaining the productivity of tropical soils, providing energy and substrate for the biological activity and modifying the physical and chemical characteristics that ensure the maintenance of soil quality and the sustainability of ecosystems. This study assessed the medium-term effect (six years) of the application of five organic composts, produced by combining different agro-industrial residues, on accumulation and chemical characteristics of soil organic matter. Treatments were applied in a long-term experiment of organic management of mango (OMM) initiated in 2005 with a randomized block design with four replications. Two external areas, one with conventional mango cultivation (CMM) and the other a fragment of regenerating Caatinga vegetation (RCF), were used as reference areas. Soil samples were collected in the three management systems from the 0.00-0.05, 0.05-0.10, and 0.10-0.20 m layers, and the total organic carbon content and chemical fractions of organic matter were evaluated by determining the C contents of humin and humic and fulvic acids. Organic compost application significantly increased the contents of total C and C in humic substances in the experimental plots, mainly in the surface layer. However, compost 3 (50 % coconut bagasse, 40 % goat manure, 10 % castor bean residues) significantly increased the level of the non-humic fraction, probably due to the higher contents of recalcitrant material in the initial composition. The highest increases from application of the composts were in the humin, followed by the fulvic fraction. Compost application increased the proportion of higher molecular weight components, indicating higher stability of the organic matter.

Effect of castor cake and elephant grass composting on edaphic fauna

Elephant grass and castor cake when combined can make a promising organic fertilizer. However, castor cake contains potentially toxic chemicals, such as ricin and ricinine. To test potential effects of these chemicals, compost piles of elephant grass ( Pennisetum purpureum Schum.) with castor cake were prepared with different C:N ratios (T1 = 40, T2 = 30, T3 = 20; T4 = 30 [control, elephant grass + crotalaria]) to evaluate colonization by edaphic fauna and any suppressive effects of castor cake. Soil organisms were collected with Berlese-Tullgren funnels. There were temporal differences between the treatments, and the epigeous fauna was mainly represented by members of the Acari and Entomobryomorpha. Elapsed time is the major factor in determining the composition of the epigeous fauna community associated with composting, indicating that castor cake has no suppressive effect.

Adubação de capim-elefante com composto orgânico produzido com resíduos animais.

A utilização do composto orgânico proveniente de resíduos da criação e abate de pequenos ruminantes pode elevar a produção de matéria seca do capim-elefante, tendo em vista o teor de nutrientes contidos nesse fertilizante orgânico, diminuindo os impactos da produção animal sobre o ambiente e reduzindo os custos de produção na área de capineira de capim-elefante. Dada à escassez de informações na literatura e a importância do manejo adequado da adubação orgânica na agropecuária, objetivou-se avaliar os atributos químicos e físicos do solo, o estado nutricional e a produção do capim-elefante submetido à aplicação de doses do composto orgânico proveniente de resíduos da produção e abate de pequenos ruminantes. O delineamento experimental adotado foi em parcelas subdivididas, com medidas repetidas no tempo, sendo as parcelas as doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1) de composto orgânico e um tratamento adicional com adubos minerais e as subparcelas os ciclos (1, 2, 3 e 4) com 4 blocos, totalizando 28 parcelas. As variáveis mensuradas foram atributos físicos e químicos do solo, a diagnose foliar e a produtividade de capim-elefante. Para o fator ciclo, a adubação orgânica incrementou a umidade gravimétrica e umidade volumétrica e ainda houve diminuição da densidade de partículas em função dos ciclos. Com as doses do fertilizante orgânico houve aumento nas concentrações da matéria orgânica, amônio, nitrato, amônio + nitrato, fósforo e saturação por base; houve redução do valor da acidez potencial, além da elevação dos teores de nitrogênio e fósforo nas plantas. As doses de composto orgânico aumentaram a biomassa de forragem total de capimelefante. A adubação mineral proporcionou maior incremento da produção do capim em relação à adubação orgânica no decorrer dos ciclos. Abstract: The use of organic compost from residues of production and slaughter of small ruminants can increase dry matter production of elephant grass, in due function of quantity nutrients in this compost, thus reducing the animal production impacts in the environment and production costs in elephant grass fields. Due to the Lack of information in literature and the importance regarding organic fertilization in agriculture, the aim of this work was evaluate chemical and physical soil attributes, nutritional status in plants and production of elephant grass in function of doses of organic compound of residues of production and slaughter of small ruminants. The experimental design was in split-plot, with the main treatment the doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1 ) of organic compost and one additional treatment with mineral fertilization and secondary treatments was the cycles (1, 2, 3 and 4) with 4 blocks, and 28 plots. The measured variables were physical and chemical attributes in the soil, nutritional diagnosis in plants and production of elephant grass. For cycle factor the organic fertilization increased gravimetric and volumetric humidity, yet, occurred decrease of density in function of cycles. With the doses of organic compost increased organic matter, ammonium, nitrate, ammonium + nitrate, phosphor and base saturation; and decreased the value of potential acidity; and increased content of N and P in plants. The doses of organic compost increased the elephant grass production. The mineral fertilization increased the elephant grass production in relation of organic fertilization over the cycles.

Characterization of the volatile profile of Brazilian Merlot wines through comprehensive two dimensional gas chromatography time-of-flight mass spectrometric detection.

Wine aroma is an important characteristic and may be related to certain specific parameters, such as raw material and production process. The complexity of Merlot wine aroma was considered suitable for comprehensive two-dimensional gas chromatography (GCGC), as this technique offers superior performance when compared to one-dimensional gas chromatography (1D-GC). The profile of volatile compounds of Merlot wine was, for the first time, qualitatively analyzed by HS-SPME-GCxGC with a time-of-flight mass spectrometric detector (TOFMS), resulting in 179 compounds tentatively identified by comparison of experimental GCxGC retention indices and mass spectra with literature 1D-GC data and 155 compounds tentatively identified only by mass spectra comparison. A set of GCGC experimental retention indices was also, for the first time, presented for a specific inverse set of columns. Esters were present in higher number (94), followed by alcohols (80), ketones (29), acids (29), aldehydes (23), terpenes (23), lactones (16), furans (14), sulfur compounds (9), phenols (7), pyrroles (5), C13-norisoprenoids (3), and pyrans (2). GCxGC/TOFMS parameters were improved and optimal conditions were: a polar (polyethylene glycol)/medium polar (50% phenyl 50% dimethyl arylene siloxane) column set, oven temperature offset of 10ºC, 7 s as modulation period and 1.4 s of hot pulse duration. Co-elutions came up to 138 compounds in 1D and some of them were resolved in 2D. Among the coeluted compounds, thirty-three volatiles co-eluted in both 1D and 2D and their tentative identification was possible only due to spectral deconvolution. Some compounds that might have important contribution to aroma notes were included in these superimposed peaks. Structurally organized distribution of compounds in the 2D space was observed for esters, aldehydes and ketones, alcohols, thiols, lactones, acids and also inside subgroups, as occurred with esters and alcohols. The Fischer Ratio was useful for establishing the analytes responsible for the main differences between Merlot and non-Merlot wines. Differentiation among Merlot wines and wines of other grape varieties were mainly perceived through the following components: ethyl dodecanoate, 1-hexanol, ethyl nonanoate, ethyl hexanoate, ethyl decanoate, dehydro-2-methyl-3(2H)thiophenone, 3-methyl butanoic acid, ethyl tetradecanoate, methyl octanoate, 1,4 butanediol, and 6-methyloctan-1-ol.