Wet Oxidation of TMP Concentrated Paper Mill Process Water. Kinetics of the reaction

Työn tarkoituksena oli tutkia lämpötilan, paineen, pH:n ja katalyytin vaikutusta paperitehtaan TMP-konsentroidun prosessiveden märkähapetuksessa. Teoriaosio sisältää katsauksen sellu- ja paperiteollisuuteen, jätevesien käsittelyyn, nanosuodatuksen ja märkähapetusprosessin toimintaperiaatteet ja sovellukset hybriditeknologialle nanosuodatus-märkähapetuksessa. Empiirinen osa koostuu märkähapetuskokeista eri lämpötiloissa, paineissa, pH:ssa ja eri katalyyseillä. Työssä tutkittiin näiden vaikutusta kemialliseen hapenkulutukseen (COD), Biologiseen hapenkulutukseen (BOD), Välittömästi saatavana olevan biologisen hapenkulutukseen (IABOD), ligniiniin, täysin orgaanisen hiileen (TOC) ja rasvaliukoisten uuteaineiden (LWEs) pitoisuuteen. Tuloksina kokeellisesta työstä saatiin korkeimmat COD:n alenemat ja BOD/COD (biohajoavuus) suurimmilla lämpötilaolosuhteilla (COD:n alenema 70 % ja BOD/COD 97 % 200 °C:ssa ja hapen 10 bar osapaineella). Tutkimuksessa, jossa selvitettiin hapen osapaineen vaikutusta saatiin tuloksena, että hapen osapaineen kasvu parantaa orgaanisen kuormituksen poistoa: COD poisto oli olosuhteilla130°C, 5bar 5 %, olosuhteilla 130 °C, 15bar 15 %, olosuhteilla 170 °C, 5bar 20 % ja olosuhteilla 170 °C, 15bar 50 %. Lähes täydellinen LWEs –poisto saavutettiin 150 °C ja 10bar olosuhteilla, vaikka tässä lämpötilassa ei saavutettu korkeata orgaanisen kuormituksen poistoa. Emäksinen pH vaikutti suosivan hapettavia reaktioita, koska korkein COD:n poisto saavutettiin näissä olosuhteilla; kuitenkin alkalisen väliaineen tehokkuudelle löydettiin tärkeä lämpötilariippuvuus.

Nymphicidal effect of vegetal extracts of Annona mucosa and Anonna crassiflora (Magnoliales, Annonaceae) against rice stalk stink bug, Tibraca limbativentris (Hemiptera, Pentatomidae)

This study aimed to verify the chloroform-methanol nymphicidal action of extracts of Annona mucosa leaves and seeds and of A. crassiflora seeds on second instar nymphs of rice stalk stink bug, Tibraca limbativentris. For each extract the concentrations of 0.5%, 1.0%, 2.0%, 4.0%, 8.0%, and two control treatments (water and Tween80®) were used. The results show that the seed extracts of A. mucosa and A. crassiflora have insecticidal activity against the T. limbativentris nymphs with statistical significance for all concentrations when compared with controls. The seed extract of A. mucosa showed the higher toxicity with greater than 75% mortality at a concentration of 1.0% in the first 24 h after application. The leaf extract of A. mucosa presented the lowest toxicity with no more than 40% mortality. The seed extract of A. crassiflora showed intermediate toxicity among all the tested extracts, and the nymph's mortality exceeded 80% for the highest concentration after 120 h of application. Considering these results, we were able to observe that the seeds extract of A. mucosa may be an alternative for the control of bed bug nymphs T. limbatriventris, especially for small producers.

Soluble sugars and germination of Annona emarginata (Schltdl.) H. Rainer seeds submitted to immersion in GA3 up to different water contents

The objective of this study was to evaluate the effect of different water contents achieved by Annona emarginata (Schltdl.) H. Rainer seeds during immersion in GA3 solutions, in variation of soluble sugars levels and germination. Seeds with 10% of initial water content were submitted to imbibition in GA3 solutions with concentrations of 0; 250; 500; 750 and 1000 mg L-1 and when they reached the water content of 15%, 20%, 25%, 30% and 35%, the quantification of soluble sugars levels and germination test were performed. Seeds immersed up to they reach 15% of water with GA3 and immersed up to the water acquisition of 20% without GA3, presented higher soluble sugars levels and germination percentage, which were decreased when the seeds reached 30% and 35% of water, independently of the presence of the plant growth regulator. It was conclude that different water contents reached by the seeds in immersion treatments with GA3 affect the soluble sugars levels and germination percentage of Annona emarginata seeds. Thus, in treatments with Annona emarginata, the seeds must remain immersed in water without GA3 up to they reach 20% of water, as higher water contents (35%) reduce the soluble sugars levels and the seed germination percentage.

Aluminium fouling and its impact on activated carbon based dioxin and furan removal in a wet scrubber at a co-incineration plant

Dioxins and furans, PCDD/Fs, are highly toxic substances formed in post combustion zones in furnaces. PCDD/F emissions are regulated by a waste incineration directive which relates also to co-incineration plants. Several observations of dioxin and furan enhancements in wet scrub- bers have been reported previously. This is thought to be due to the so-called "memory effect" which occurs when dioxins and furans absorb into plastic material in scrubbers and desorb when ambient circumstances alter significantly. At the co-incineration plant involved, dioxins and furans are controlled with a wet scrubber, the tower packing of which is made of plastic in which activated carbon particles are dispersed. This should avoid the memory effect and act as a dioxin and furan sink since dioxins and furans are absorbed irreversibly into the packing ma- terial. In this case, the tower packing in the scrubber is covered with a white layer that has been found to be mainly aluminium. The aim of this thesis was to determine the aluminium balance and the dioxin and furan behaviour in the scrubber and, thus, the impacts that the foul- ing has on dioxin and furan removal. The source of aluminium, reasons for fouling and further actions to minimize its impacts on dioxin and furan removal were also to be discovered. Measurements in various media around the scrubber and in fuels were made and a profile analysis of PCDD/F and mass balance calculations were carried out. PCDD/F content de- creased in the scrubber. The reduced PCDD/F was not discharged into scrubbing water. The removal mechanism seems to work in spite of the fouling, at least with low PCDD/F loads. Most of the PCDD/F in excess water originates from the Kymijoki River which is used as feeding water in the scrubber. Fouling turned out to consist mainly of aluminium hydroxides. Sludge combusted in the furnace was found to be a significant source of aluminium. Ways to minimize the fouling would be adjustment of pH to a proper lever, installation of a mechanical filter to catch the loose material from the scrubbing water and affecting the aluminium content of the sludge.

Characterization and genetic mapping of eceriferum-ym (cer-ym), a cutin deficient barley mutant with impaired leaf water retention capacity.

The cuticle covers the aerial parts of land plants, where it serves many important functions, including water retention. Here, a recessive cuticle mutant, eceriferum-ym (cer-ym), of Hordeum vulgare L. (barley) showed abnormally glossy spikes, sheaths, and leaves. The cer-ym mutant plant detached from its root system was hypersensitive to desiccation treatment compared with wild type plants, and detached leaves of mutant lost 41.8% of their initial weight after 1 h of dehydration under laboratory conditions, while that of the wild type plants lost only 7.1%. Stomata function was not affected by the mutation, but the mutant leaves showed increased cuticular permeability to water, suggesting a defective leaf cuticle, which was confirmed by toluidine blue staining. The mutant leaves showed a substantial reduction in the amounts of the major cutin monomers and a slight increase in the main wax component, suggesting that the enhanced cuticle permeability was a consequence of cutin deficiency. cer-ym was mapped within a 0.8 cM interval between EST marker AK370363 and AK251484, a pericentromeric region on chromosome 4H. The results indicate that the desiccation sensitivity of cer-ym is caused by a defect in leaf cutin, and that cer-ym is located in a chromosome 4H pericentromeric region.

Headspace needle-trap analysis of priority volatile organic compounds from aqueous samples: application to the analysis of natural and waste waters

Combining headspace (HS) sampling with a needle-trap device (NTD) to determine priority volatile organic compounds (VOCs) in water samples results in improved sensitivity and efficiency when compared to conventional static HS sampling. A 22 gauge stainless steel, 51-mm needle packed with Tenax TA and Carboxen 1000 particles is used as the NTD. Three different HS-NTD sampling methodologies are evaluated and all give limits of detection for the target VOCs in the ng L−1 range. Active (purge-and-trap) HS-NTD sampling is found to give the best sensitivity but requires exhaustive control of the sampling conditions. The use of the NTD to collect the headspace gas sample results in a combined adsorption/desorption mechanism. The testing of different temperatures for the HS thermostating reveals a greater desorption effect when the sample is allowed to diffuse, whether passively or actively, through the sorbent particles. The limits of detection obtained in the simplest sampling methodology, static HS-NTD (5 mL aqueous sample in 20 mL HS vials, thermostating at 50 °C for 30 min with agitation), are sufficiently low as to permit its application to the analysis of 18 priority VOCs in natural and waste waters. In all cases compounds were detected below regulated levels

Concerted changes in N and C primary metabolism in alfalfa (Medicago sativa) under water restriction

Although the mechanisms of nodule N2 fixation in legumes are now well documented, some uncertainty remains on the metabolic consequences of water deficit. In most cases, little consideration is given to other organs and, therefore, the coordinated changes in metabolism in leaves, roots, and nodules are not well known. Here, the effect of water restriction on exclusively N2-fixing alfalfa (Medicago sativa L.) plants was investigated, and proteomic, metabolomic, and physiological analyses were carried out. It is shown that the inhibition of nitrogenase activity caused by water restriction was accompanied by concerted alterations in metabolic pathways in nodules, leaves, and roots. The data suggest that nodule metabolism and metabolic exchange between plant organs nearly reached homeostasis in asparagine synthesis and partitioning, as well as the N demand from leaves. Typically, there was (i) a stimulation of the anaplerotic pathway to sustain the provision of C skeletons for amino acid (e.g. glutamate and proline) synthesis; (ii) re-allocation of glycolytic products to alanine and serine/glycine; and (iii) subtle changes in redox metabolites suggesting the implication of a slight oxidative stress. Furthermore, water restriction caused little change in both photosynthetic efficiency and respiratory cost of N2 fixation by nodules. In other words, the results suggest that under water stress, nodule metabolism follows a compromise between physiological imperatives (N demand, oxidative stress) and the lower input to sustain catabolism.

Reduction and Analysis Methods of Indigo

Throughout history indigo was derived from various plants for example Dyer’s Woad (Isatis tinctoria L.) in Europe. In the 19th century were the synthetic dyes developed and nowadays indigo is mainly synthesized from by-products of fossil fuels. Indigo is a so-called vat dye, which means that it needs to be reduced to its water soluble leucoform before dyeing. Nowadays, most of the industrial reduction is performed chemically by sodium dithionite. However, this is considered environmentally unfavourable because of waste waters contaminating degradation products. Therefore there has been interest to find new possibilities to reduce indigo. Possible alternatives for the application of dithionite as the reducing agent are biologically induced reduction and electrochemical reduction. Glucose and other reducing sugars have recently been suggested as possible environmentally friendly alternatives as reducing agents for sulphur dyes and there have also been interest in using glucose to reduce indigo. In spite of the development of several types of processes, very little is known about the mechanism and kinetics associated with the reduction of indigo. This study aims at investigating the reduction and electrochemical analysis methods of indigo and give insight on the reduction mechanism of indigo. Anthraquinone as well as it’s derivative 1,8-dihydroxyanthraquinone were discovered to act as catalysts for the glucose induced reduction of indigo. Anthraquinone introduces a strong catalytic effect which is explained by invoking a molecular “wedge effect” during co-intercalation of Na+ and anthraquinone into the layered indigo crystal. The study includes also research on the extraction of plant-derived indigo from woad and the examination of the effect of this method to the yield and purity of indigo. The purity has been conventionally studied spectrophotometrically and a new hydrodynamic electrode system is introduced in this study. A vibrating probe is used in following electrochemically the leuco-indigo formation with glucose as a reducing agent.

Thermal-Hydraulic Studies on the Safety Of VVER-440 Type Nuclear Power Plants

This thesis includes several thermal hydraulic analyses related to the Loviisa WER 440 nuclear power plant units. The work consists of experimental studies, analysis of the experiments, analysis of some plant transits and development of a calculational model for calculation of boric acid concentrations in the reactor. In the first part of the thesis, in the case of won of boric acid solution behaviour during long term cooling period of LOCAs, experiments were performed in scaled down test facilities. The experimental data together with the results of RELAPS/MOD3 simulations were used to develop a model for calculations of boric acid concentrations in the reactor during LOCAs. The results of calculations showed that margins to critical concentrations that would lead to boric acid crystallization were large, both in the reactor core and in the lower plenum. This was mainly caused by the fact that water in the primary cooling circuit includes borax (Na)BsO,.IOHZO), which enters the reactor when ECC water is taken from the sump and greatly increases boric acid solubility in water. In the second part, in the case of simulation of horizontal steam generators, experiments were performed with PACTEL integral test loop to simulate loss of feedwater transients. The PACTEL experiments, as well as earlier REWET III natural circulation tests, were analyzed with RELAPS/MOD3 Version Sm5 code. The analysis showed that the code was capable of simulating the main events during the experiments. However, in the case of loss of secondary side feedwater the code was not completely capable to simulate steam superheating in the secondary side of the steam generators. The third part of the work consists of simulations of Loviisa VVER reactor pump trip transients with RELAPSlMODI Eur, RELAPS/MOD3 and CATHARE codes. All three codes were capable to simulate the two selected pump trip transients and no significant differences were found between the results of different codes. Comparison of the calculated results with the data measured in the Loviisa plant also showed good agreement.

How are riparian plants distributed along the riverbank topographic gradient in Mediterranean rivers? Application to minimally altered river stretches in Southern Spain.

Species structure and composition in Mediterranean riparian forests are determined by hydrological features, longitudinal zonation, and riverbank topography. This study assesses the distribution of four native riparian plants along the riverbank topographic gradient in three river stretches in southern Spain, with special emphasis on the occupation of adult and young feet of each species. The studied stretches suffered minimal human disturbances, displayed semi-arid conditions, and had wide riparian areas to allow the development of the target species: black alder (Alnus glutinosa), salvia leaf willow (Salix salviifolia), narrow-leafed ash (Fraxinus angustifolia), and oleander (Nerium oleander). Thalweg height was used to define the riverbank topographic gradient. The results showed a preferential zone for black alder and salvia leaf willow in the range of 0-150 cm from the channel thalweg, with adult alders and willows being more common between 51 and 150 cm and young alders being more common under 50 cm. Conversely, narrow-leafed ash and oleander were much more frequent, and showed greater development, in the ranges of 151-200 cm and 201-250 cm, respectively, whereas the young feet of both species covered the entire topographic range. Adult feet of the four species were spatially segregated along the riverbank topographic gradient, indicating their differential ability to cope with water stress from the non-tolerant alders and willows to more tolerant narrow-leafed ash trees and oleanders. Young feet, however, showed a strategy more closely linked to the initial availability of colonisation sites within riparian areas to the dispersion strategy of each species and to the distribution of adult feet. In Mediterranean areas, where riparian management has traditionally faced great challenges, the incorporation of species preferences along riverbank gradients could improve the performance of restoration projects.

Recent research data on the removal of pharmaceuticals from sewage treatment plants (STP)

Pharmaceutical compounds have been detected in sewage treatment plant (STP) effluents, surface waters and, less frequently, in groundwater and drinking water, all over the world. Different sources are responsible for their appearance in the aquatic environment, however, it is widely accepted that the main sources of this type of pollutant are STP effluents. The adverse effects of pharmaceuticals in the environment include aquatic toxicity, development of resistance in pathogenic bacteria, genotoxicity and endocrine disruption. Thus, the discharge of these compounds to the environment in STP effluents should be minimized.

Ultrafiltration membranes from waste polyethylene terephthalate and additives: synthesis and characterization

The synthesis and characterization of asymmetric ultrafiltration membranes from recycled polyethylene terephthalate (PET) and polyvinylpyrrolidone (PVP) is reported. PET is currently used in many applications, including the manufacture of bottles and tableware. Monomer extraction from waste PET is expensive, and this process has not yet been successfully demonstrated on a viable scale. Hence, any method to recycle or regenerate PET once it has been used is of significant importance from scientific and environmental research viewpoints. Such a process would be a green alternative due to reduced raw monomer consumption and the additional benefit of reduced manufacturing costs. The membranes described here were prepared by a phase-inversion process, which involved casting a solution containing PET, m-cresol as solvent, and polyethylene glycol (PEG) of different molecular weights as additives. The membranes were characterized in terms of pure water permeability (PWP), molecular weight cut-off (MWCO), and flux and membrane morphology. The results show that the addition of PEG with high molecular weights leads to membranes with higher PWP. The presence of additives affects surface roughness and membrane morphology.

EFEITO DOS TRATAMENTOS SUPERFICIAIS NAS PROPRIEDADES DO BAGAÇO DA FIBRA DE PIAÇAVA Attalea funifera Martius

The aim of this study was to investigate the effect of surface treatment on the properties of waste piassava fiber with the goal of aggregating additional business value. The fiber surface was subjected to four different treatments. In the present work, it was found that washing the fibers with water partially removed impurities from the surface rendering it rougher. Alkaline treatment removed impurities from the surface, hemicellulose and lignin, improving the flexibility of the fibers. Increasing the concentration of washing agents, times and temperature of treatment promoted intense defibrillation on the fiber surface, reducing its strength.

Cuticular and Suberin Polymers of Edible Plants. Analysis by Gas Chromatographic-Mass Spectrometric and Solid State Spectroscopic Methods

Cutin and suberin are structural and protective polymers of plant surfaces. The epidermal cells of the aerial parts of plants are covered with an extracellular cuticular layer, which consists of polyester cutin, highly resistant cutan, cuticular waxes and polysaccharides which link the layer to the epidermal cells. A similar protective layer is formed by a polyaromatic-polyaliphatic biopolymer suberin, which is present particularly in the cell walls of the phellem layer of periderm of the underground parts of plants (e.g. roots and tubers) and the bark of trees. In addition, suberization is also a major factor in wound healing and wound periderm formation regardless of the plants’ tissue. Knowledge of the composition and functions of cuticular and suberin polymers is important for understanding the physiological properties for the plants and for nutritional quality when these plants are consumed as foods. The aims of the practical work were to assess the chemical composition of cuticular polymers of several northern berries and seeds and suberin of two varieties of potatoes. Cutin and suberin were studied as isolated polymers and further after depolymerization as soluble monomers and solid residues. Chemical and enzymatic depolymerization techniques were compared and a new chemical depolymerization method was developed. Gas chromatographic analysis with mass spectrometric detection (GC-MS) was used to assess the monomer compositions. Polymer investigations were conducted with solid state carbon-13 cross polarization magic angle spinning nuclear magnetic resonance spectroscopy (13C CP-MAS NMR), Fourier transform infrared spectroscopy (FTIR) and microscopic analysis. Furthermore, the development of suberin over one year of post-harvest storage was investigated and the cuticular layers from berries grown in the North and South of Finland were compared. The results show that the amounts of isolated cuticular layers and cutin monomers, as well as monomeric compositions vary greatly between the berries. The monomer composition of seeds was found to differ from the corresponding berry peel monomers. The berry cutin monomers were composed mostly of long-chain aliphatic ω-hydroxy acids, with various mid-chain functionalities (double-bonds, epoxy, hydroxy and keto groups). Substituted α,ω-diacids predominated over ω-hydroxy acids in potato suberin monomers and slight differences were found between the varieties. The newly-developed closed tube chemical method was found to be suitable for cutin and suberin analysis and preferred over the solvent-consuming and laborious reflux method. Enzymatic hydrolysis with cutinase was less effective than chemical methanolysis and showed specificity towards α,ω-diacid bonds. According to ₁₃C CP-MAS NMR and FTIR, the depolymerization residues contained significant amounts of aromatic structures, polysaccharides and possible cutan-type aliphatic moieties. Cultivation location seems to have effect on cuticular composition. The materials studied contained significant amounts of different types of biopolymers that could be utilized for several purposes with or without further processing. The importance of the so-called waste material from industrial processes of berries and potatoes as a source of either dietary fiber or specialty chemicals should be further investigated in detail. The evident impact of cuticular and suberin polymers, among other fiber components, on human health should be investigated in clinical trials. These by-product materials may be used as value-added fiber fractions in the food industry and as raw materials for specialty chemicals such as lubricants and emulsifiers, or as building blocks for novel polymers.

Physiological cost of induced resistance in cotton plants at different nitrogen levels

Resistance induction through the use of chemical inducers often results in physiological costs to the plant. In this study, induced resistance in cotton plants was evaluated with regard to physiological costs in a cultivar susceptible to Colletotrichum gossypii var. cephalosporioides (CNPA GO 2002 - 7997). Plants were cultivated in substrates with two levels of nitrogen and received two applications of acibenzolar-S-methyl (ASM), jasmonic acid (JA) and Agro-Mos® (AM) disease resistance inducers. Plant height (H), internodal length (IL), shoot fresh weight (SFW), root fresh weight (RFW), shoot dry weight (SDW) and root dry weight (RDW) were evaluated. The activity of the phenylalanine ammonia lyase (PAL) and peroxidase (POX) was also determined. The plants treated with ASM presented high physiological costs with an accentuated reduction in H, SFW and SDW, whereas those treated with JA exhibited a significant increase in SDW, and did not significantly differ from H and IL. In the potting mix supplemented with nitrogen, all inducers differed from the control treatment regarding to internodal length, whereas only ASM and AM presented a significant difference between one another in the potting mix without the addition of nitrogen. Significant correlations (P=0.05) were found for most of the variables analyzed, with greater correlations observed between SFW and SDW (0.94); IL and H (0.74); SFW and H (0.70); and SDW and H (0.70). ASM induced the least amount of PAL activity, significantly differing from the remaining treatments. Greater POX activity was observed in ASM, which significantly differed from the control. AM and JA, however, presented lower activity than the control with regard to these enzymes, and it was not possible to confirm induction resistance in these two treatments.