The bioessential trace metals (e.g. zinc, copper and iron) are primarily excreted via the gastrointestinal trace in normal man and animals. Although urinary losses of these trace metals are usually minimal, they have been reported to be markedly elevated during periods of physiological and pathological stress. The possibility that the decreased plasma insulin to glucagon ratio during episodes of stress is responsible for increased urinary trace metal excretion was examined in normal and streptozotocin-diabetic rats. Induction of the diabetic condition resulted in a rapid and persistent increase in the quantities of zinc, copper and iron lost in the urine daily. Diabetic rats excreted 3.4, 5.0, and 4.9-fold more zinc, copper and iron, respectively, at 14 days after injection with the diabetogenic drug than the controls. Insulin treatment of diabetic rats significantly reduced the daily urinary losses of these micronutrients, indicating that altered hormonal balance was the primary cause for elevated urinary excretion. Enhanced urinary losses of these metals were not associated with decreased concentrations of zinc, copper and iron in plasma, liver and kidney. Various processes, including the filterability of the metal, glomerular filtration rate, renal tubular reabsorption and transtubular secretion have been reported to influence urinary excretion of trace metals. Initial studies have been conducted to assess the influence of altered endocrine status on the characteristics of zinc binding and transport by renal brush border membrane vesicles (BBMV) in vitro. The accumulation of zinc by BBMV was found to be temperature dependent. No apparent differences in the binding and intravesicular accumulation of zinc by brush border membrane vesicles prepared from normal and STZ-diabetic rats were observed. Likewise, the efflux of zinc from BBMV prepared from control and diabetic renal cortex was similar. These results indicated that the potential for zinc reabsorption is not altered in the diabetic rats. In vivo studies are required to further assess the characteristics of zinc reabsorption in the native milieu. / M.S.

Food waste is a desirable feedstock for anaerobic digestion because it is high in moisture and is an easily degradable material. However, mono-digestion of food waste often fails due to the accumulation of volatile fatty acids. Supplementing trace elements is one strategy to combat this issue. This study examined the effect of supplementing trace elements (iron, nickel, selenium, molybdenum, magnesium, zinc, calcium, copper, manganese, cobalt) on the methane yield and organic waste destruction of anaerobically digested food waste. Methane yield of food waste with and without the inorganic salt trace element was determined by the gas density-based biomethane potential method at mesophilic (37°C) conditions over 30 days. The three treatments were inoculum only, food waste and inoculum, and food waste and inoculum with an added trace element solution. There was no significant difference between treatments in terms of waste stabilization (percent volatile solids, total solids, and total chemical oxygen demand reduction) between treatments. The average cumulative biogas produced was 41% higher, and the average total cumulative methane produced was 23% higher in the treatment with the trace element supplement. Mean methane yield was not different (p > 0.05) between treatments over the 30 days, and there was no difference (p > 0.05) in biomethane potential between treatments. In addition, greenhouse gas reduction potential was estimated from food waste streams in Montgomery, VA using anaerobic digestion. The purpose of this work was to (1) estimate the total mass of food waste produced in Montgomery, VA in a year, (2) use the results from the biomethane potential analyses to inform the sizing of a theoretical community digester in Montgomery, VA, and (3) estimate the greenhouse gas reduction potential of anaerobically digesting the food waste instead of sending it to landfill. Greenhouse gas reduction was calculated using the Climate Action Reserve Organic Waste Digestion Project Protocol guidelines. The greenhouse gas reduction potential was estimated as 6,532 tonnes of carbon dioxide equivalent per year (tCO2e/year), with approximately 693 m3 methane produced per day. In one year, the digester would generate an estimated 7370 kWh of energy which has the potential to power 149 homes for a year in Montgomery, VA. In addition, 4130 tonnes/year of composted digestate would be available as fertilizer for surrounding farms. / Master of Science / Currently, about one-third of the entire U.S. food supply is lost or wasted. A large portion of that food waste is sent to landfills, where it produces methane, a greenhouse gas. Instead, food waste can be broken down to produce biogas during anaerobic digestion. Anaerobic digestion is a process in which microorganisms break down organic materials in the absence of oxygen to produce biogas and digestate, a material used as a soil amendment or fertilizer. However, anaerobically digesting food waste often leads to process instability and failure due to a buildup of undesirable intermediates. Microorganisms in anaerobic digestion require certain trace elements (i.e., iron, copper) that food waste often lacks; therefore, supplementing key trace elements may improve the anaerobic digestion of food waste. This research aimed to assess the effect of supplementing key trace elements (iron, copper, zinc, calcium, magnesium, nickel, manganese, selenium, molybdenum, cobalt) on organic matter degradation and methane yield. Methane yield of food waste with and without the inorganic salt trace element was determined by the gas density-based biomethane potential method at mesophilic (37°C) conditions over 30 days. The average cumulative biogas produced was 41% higher, and the average total cumulative methane produced was 23% higher in the bottles containing a trace element supplement. No significant difference was seen in the two groups when comparing organic matter degradation. These results demonstrate that supplementing trace elements can improve biogas and methane production. Greenhouse gas reductions from anaerobically digesting food waste instead of sending it to landfills were determined for Montgomery, VA. The results from the biomethane potential test informed the design of a theoretical community digester. Greenhouse gas reduction was calculated using the Climate Action Reserve Organic Waste Digestion Project Protocol equations. The greenhouse gas reduction was determined as 6,532 tonnes of carbon dioxide equivalent per year (tCO2e/year). The digester would produce approximately 693 m3 methane/day, which has the potential to power 149 homes for a year in Montgomery, VA. In addition, 4130 tonnes/year of compost would be produced and available as a fertilizer for surrounding farms.

No / Dietary ecology is one key to understanding the biology, lifeways, and evolutionary pathways of many animals. Determining the diets of long-extinct hominins, however, is a considerable challenge. Although archaeological evidence forms a pillar of our understand-ing of diet and subsistence in the more recent past, for early hominins, the most direct evidence is to be found inthe fossils themselves. Here we review the suite of emerging biochemical paleodietary tools based on stable isotopeand trace element archives within fossil calcified tissues.We critically assess their contribution to advancing our understanding of australopith, early Homo, and Neander-thal diets within the broader context of non-biogeochemical techniques for dietary reconstruction, such as mor-phology and dental microwear analysis. The most signifi-cant outcomes to date are the demonstration of hightrophic-level diets among Neanderthals and Late Pleistocene modern humans in Glacial Europe, and the persis-tent inclusion of C4 grass-related foods in the diets of Plio¿Pleistocene hominins in South Africa. Such studies clearly show the promise of biogeochemical techniques for testing hypotheses about the diets of early hominins.Nevertheless, we argue that more contextual data from modern ecosystem and experimental studies are needed if we are to fully realize their potential.

The potential of Arctica islandica, a long lived marine bivalve with a lifespan of over 300 years, to reconstruct a high resolution (sub-annual) climate record is explored in this thesis. Fluctuations in trace element and isotopic data from live-collected specimens from Irvine Bay, NW Scotland are compared to instrumental (particularly temperature) data. X-ray absorption spectroscopy data demonstrate the coordination state of Sr and Mg within the shell. These are consistent with models in which Sr substitutes ideally for Ca in aragonite, and Mg is bound predominantly to organic molecules. Sr/Ca incorporation may be influenced by changes in the crystal nucleation, propagation and growth rate as well as vital effects. However any effect of seawater temperature on Sr/Ca incorporation was obscured by these other factors. Mg concentration is not a linear function of a single environmental variable or organic content within the shell, indicating that Mg uptake is biologically mediated. Ba variation shows sporadic increases (of >500% above baseline) in both shells, the timing of which is similar between the prismatic layer and umbo region. The maxima are, however, not synchronous between the two shells analysed. The controls on Ba uptake require further research, but low Ba/Ca may reflect Ba/Ca concentrations within the seawater. Aliquots taken from cod otoliths show that micromilling has negligible effect on δ¹⁸O. The range of reconstructed temperature from δ¹⁸O profiles Arctica islandica shows good agreement with the sea surface temperature data from the nearby Millport marine station to within 2.1 °C. However, both the interannual and intra-annual variation appears to be sensitive to changes in temporal resolution resulting from changes in growth rates. Modelling of δ¹⁸O highlights dependence on changes in temporal resolution of the sampling, in addition to temperature and salinity. Results from the radiocarbon pilot study show that Arctica islandica is a suitable archive for changes in radiocarbon associated with anthropogenic ¹⁴C fluxes.

Afin d'établir l'impact et le risque lié aux fertilisants chimiques depuis leur fabrication jusqu'à leur amendement sur la contamination des sols par les éléments traces métalliques, une étude de leur mobilité et leur transfert s'avère nécessaire. L'objectif de ce travail de thèse était d'évaluer la source de contamination du sol par les éléments traces autour de l'industrie des fertilisants chimiques et suivre l'évolution temporelle de la mobilité et du transfert de ces éléments dans un profil du sol agricole amendé par des engrais phosphatés du type simple superphosphate (SSP) ou du phosphogypse. Pour cela nous avons utilisé des techniques permettant la caractérisation structurale et minéralogique des sols collectés comme la diffraction des rayons X et la microscopie électronique. Puis une caractérisation chimique des sols collectés concernant la concentration totale des éléments traces et des éléments majeurs a été établie. Comme la mobilité n'est pas stable au cours du temps dépendant de plusieurs paramètres physico-chimiques comme le pH, le potentiel redox, la teneur en matière organique, une extraction séquentielle a été adoptée le long de l'étude au cours du temps et dans le profil du sol amendé jusqu'à une profondeur de 55 cm. En outre, l'absorption des éléments traces par les plantes cultivées sur le terrain agricole amendé par les engrais ou le phosphogypse a été analysée au cours du temps afin d'évaluer le risque lié à la chaîne alimentaire et plus particulièrement la chaîne alimentaire humaine induisant des effets négatifs sur la santé. Une comparaison entre l'application du phosphogypse et celle des engrais a été mise en évidence à la finalité de ce travail / To determine the impact and risk of chemical fertilizers, from their manufacture to their amendment, on soil contamination by trace metals, the study of their mobility and transfer would be necessary. The objective of this work was to evaluate the source of soil contamination by trace elements around the industry of chemical fertilizers, and to follow the temporal evolution of mobility and transfer of these elements in the profile of agricultural soil amended by superphosphate (SSP) fertilizers or phosphogypsum. To achieve our objective, we used techniques allowing the determination of structural and mineralogical characterization of collected soil samples, such as X-ray diffraction and electron microscopy. Chemical characterization related to the total concentration of trace and major elements of collected soils was established. As mobility was unstable over time, depending on several physico-chemical parameters such as pH, redox potential, and organic matter content, a sequential extraction was adopted throughout the study over time in the amended soil profile to a depth of 55 cm. In addition, the absorption of trace elements by agricultural crops cultivated over land amended with fertilizer or phosphogypsum was analyzed over time to assess the risk of their transfer to the food chain, especially the human food chain, imposing health hazards. A comparison between the effects of the application of phosphogypsum and phosphate fertilizer was carried out in concluding this work

O objetivo primário deste estudo é aprimorar o conhecimento acerca das fontes do manto e dos mecanismos envolvidos na gênese dos basaltos da Província Magmática do Paraná, que constitui uma das maiores manifestações de basaltos continentais do mundo. Para tanto, foram determinadas as concentrações de terras raras (La, Ce, Nd, Sm, Eu, Tb, Yb e Lu), outros elementos traço (Cs, Rb, Ba, U, Th, Ta, Hf, Co e Sc) e elementos altamente siderófilos (Os, Ir, Ru, Pt, Pd e Re), juntamente com razões isotópicas dos sistemas Rb-Sr, Sm-Nd, U-Th-Pb e Re-Os em basaltos com alto-Ti (Paranapanema e Pitanga) que ocorrem no norte da PMP. Além disso, foram determinadas as concentrações de elementos altamente siderófilos e as razões isotópicas de 187Os/188Os amostras representativas de basaltos com baixo-Ti (Esmeralda) do sul da PMP. Os dados geoquímicos e as razões isotópicas de Sr, Nd e Pb obtidos são consistentes com dados da literatura, porém, refinam as variações (extremos) isotópicas dos magmas-tipo Paranapanema e Pitanga. Esses dados, juntamente com as concentrações de elementos altamente siderófilos e das razões isotópicas de Os, inéditas na literatura, sugerem que as fontes dos basaltos (astenosfera ou manto litosférico subcontinental) sofreram metassomatismo significativo, com a intrusão de veios piroxeníticos, relacionado a antigas subducções e/ou processos de delaminação. / The primary goal of this study is to improve the understanding about the mantle sources and the mechanisms involved in the basalt genesis from Paraná Magmatic Province (PMP), which is one of the largest known continental flood basalts of the world. Therefore, the concentrations of rare earths (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu), other trace elements (Cs, Rb, Ba, U, Th, Ta, Hf, Co and Sc) and highly siderophile elements (Os, Ir, Ru, Pt, Pd and Re) were determined, along with isotope ratios regarding Rb-Sr, Sm-Nd, U-Th-Pb e Re-Os systematics in high-Ti basalts (Paranapanema and Pitanga) from northern PMP. In addition, the highly siderophile element concentrations, as well as 187Os/188Os isotope ratios, were measured in selected samples of low-Ti basalts (Esmeralda) from southern PMP. The geochemical and Sr-Nd-Pb isotope results of the present study are consistent with literature data, but refine the isotope variations (extreme) for the Paranapanema and Pitanga magma-types. These data, along with the concentrations of highly siderophile elements and Os isotope ratios suggest that the basalt mantle sources (asthenosphere or subcontinental lithospheric mantle) were affected by significant metasomatism (piroxenitic vein hybridization), related with old subduction and/or delamination processes.

Μία από τις σημαντικότερες αποθέσεις λιγνίτη της Δυτικής Τουρκίας εντοπίζεται στην λεκάνη της Mugla. Η λεκάνη της Mugla αποτελείται από δύο τάφρους ΒΔ-ΝΑ διεύθυνσης, οι οποίες χωρίζονται από μία πλατιά έξαρση του υποβάθρου, δημιουργώντας τις υπολεκάνες του Yatağan και του Milas. Η εμφάνιση του υποβάθρου αποτελείται στα νότια από τα Λυκκιακά καλύμματα, τα οποία περιλαμβάνουν ένα σύμπλεγμα πετρωμάτων ωκεάνιας και ηπειρωτικής προέλευσης και στα βόρεια από μεταμορφωμένα πετρώματα, όπως σχιστόλιθοι, γνεύσιοι, αμφιβολίτες, και μάρμαρα της Μάζας Menderes. Η παρούσα εργασία εστιάζει στο λιγνίτη της περιοχής Milas και τα στερεά παραπροϊόντα καύσης του (ιπτάμενη τέφρα και τέφρα εστίας) από τις περιοχές Yeniköy, Yatağan και Kemerköy της Τουρκίας. Σκοπός της μελέτης είναι η εκτίμηση της κινητικότητας των ιχνοστοιχείων κατά την εκμετάλλευση του λιγνίτη για ηλεκτροπαραγωγή και κατά την αποθήκευση και διάθεση των στερεών παραπροϊόντων της καύσης του στην περιοχή Mugla της Τουρκίας. Αντικείμενο της εργασίας αποτέλεσε η γεωχημική μελέτη του λιγνίτη και των παραπροϊόντων του, καθώς και η χημική μελέτη των διαλυμάτων που προέκυψαν κατά την απόπλυσή τους σε συνθήκες pH 5 και 8,5. Επιπρόσθετα, πραγματοποιήθηκε μία σειρά εργαστηριακών αναλύσεων, που περιλαμβάνουν την προσεγγιστική και στοιχειακή ανάλυση, την ανθρακοπετρογραφική εξέταση, καθώς και τις ορυκτολογικές αναλύσεις όλων των δειγμάτων. Στα πλαίσια των εργαστηριακών αναλύσεων, προσδιορίστηκε η υγρασία, η τέφρα, η περιεκτικότητα σε πτητικά συστατικά, καθώς και η περιεκτικότητα των C, H, N και S του λιγνίτη και των παραπροϊόντων του, ο μόνιμος άνθρακας, η θερμαντική ικανότητα και η ανακλαστικότητα του λιγνίτη. Οι συγκεντρώσεις των ιχνοστοιχείων στον λιγνίτη, την ιπτάμενη τέφρα και την τέφρα εστίας προσδιορίστηκαν με τη χρήση του οργάνου ELAN 6100 Perkin Elmer®. Τα στοιχεία, που προσδιορίστηκαν είναι τα Αg, As, B, Ba, Be, Co, Cr, Cu, Fe, Ga, Hf, Hg, Li, Mn, Mo, Ni, Pb, Se, Sr, U, V και Zn. Σύμφωνα με τις περιεκτικότητες των ιχνοστοιχείων του λιγνίτη και των παραπροϊόντων της καύσης του εκτιμήθηκε η κινητικότητά τους κατά την καύση με τον υπολογισμό του συντελεστή εμπλουτισμού (R.E.). Πολύ μικρό συντελεστή εμπλουτισμού και κατά συνέπεια έντονη πτητικότητα παρουσιάζουν τα στοιχεία As, Cd, Mo, Pb και Sr. Μέτρια πτητικότητα εμφανίζουν τα Ag, B, Cr, Ni, U, V, Zn, ενώ όλα τα υπόλοιπα έχουν μικρή πτητικότητα, καθώς συμμετέχουν στο τμήμα των παραπροϊόντων που παραμένει στην τέφρα των ατμοηλεκτρικών σταθμών. Ακολούθως, έλαβαν χώρα πειράματα έκπλυσης των ιχνοστοιχείων από το λιγνίτη και τα παραπροϊόντα του σε συνθήκες pH 5 και 8,5, ούτως ώστε να προσδιοριστεί η κινητικότητα τους, με τη βοήθεια του Ποσοστού Σχετικής Έκπλυσης (RML) και της Έντασης έκπλυσης (Ιl). Τα αποτελέσματα των παραπάνω έδειξαν ως πιο κινητικά ιχνοστοιχεία σε συνθήκες pH 5 και 8,5, στο λιγνίτη τα As, B, Mn, Sr, στην ιπτάμενη τέφρα τα Cr, Li, Mo και Sr, και στην τέφρα εστίας τα Li, Mo, Sr. Προκειμένου να προσδιοριστεί η γεωχημική συγγένεια των ιχνοστοιχείων στα «ως έχει» δείγματα του λιγνίτη και των παραπροϊόντων καύσης του, αλλά και να περιγραφεί η συμπεριφορά τους κατά τη διάρκεια της έκπλυσής τους σε διαφορετικές τιμές pH, πραγματοποιήθηκε στατιστική επεξεργασία των αποτελεσμάτων της στοιχειακής ανάλυσης. Ειδικότερα, στα αποτελέσματα των στοιχειακών αναλύσεων και των τιμών έκπλυσης των ιχνοστοιχείων όλων των δειγμάτων ξεχωριστά για pH 5 και pH 8,5, καθώς και των ορυκτών της ιπτάμενης τέφρας και της τέφρας εστίας εφαρμόστηκε η μέθοδος της παραγοντικής ανάλυσης R-τύπου. / One of the most important lignite deposits of Western Turkey is located in the basin of Mugla. The Mugla basin consists of two NW-SE direction grabens, which are separated by a wide rise of the basement that creates the sub-basins of Yatağan and Milas. Southern, the basement is consisted of the Lyccian nappes, which contain a cluster of ocean and continental origin rocks, while northern is consisted of metamorphic rocks, such as schists, gneiss, amphibolites and marbles of the Menderes Mass. The present study focuses on the lignite of Milas region and its combustion solid by-products (fly ash and bottom ash) from Yeniköy, Yatağan and Kemerköy areas in Turkey. The purpose of this study is to estimate the mobility of elements and trace elements in the exploitation of the lignite deposits for generating power in the region of Mugla in Turkey. The object of the present study lies in the geochemical study of lignite and its combustion products and in the determination of the mobility of trace elements during the combustion of lignite and the leaching of lignite and its by-products, under pH 5 and 8.5 conditions. In addition, several laboratory analyses are performed, including the proximate and the elemental analysis, the coal-petrographical examination and the mineralogical analysis of all samples. During these laboratory analyses are determined the moisture, the ash, the content of volatile components and the content of C, H, N and S of lignite and lignite combustion products the permanent carbon, the calorific value and the reflectivity of lignite. The contents of trace elements in lignite, in fly ash and in bottom ash are determined using an ELAN 6100 Perkin Elmer ® instrument. The elements, which were identified, are Ag, As, B, Ba, Be, Co, Cr, Cu, Fe, Ga, Hf, Hg, Li, Mn, Mo, Ni, Pb, Sr, U, V and Zn. According to the trace elements contents of lignite and its combustion products, the mobility during combustion was determined using the Enrichment Factor (RE). Very low rate of enrichment and thus, strong volatility, have the elements As, Cd, Mo, Pb and Sr. Medium volatility is being observed in the elements Ag, B, Cr, Ni, U, V, Zn, while all the rest have low volatility due to their existence in the part of the lignite co-products that remain in the ash of the Thermal Power Plants. Furthermore, leaching experiments under pH 5 and 8.5 conditions took place to estimate the mobility of trace elements from lignite and its by-products using the Relative Mass Leached (RML) and Leaching Intensity (Ιl). The above results, under pH 5 and 8.5 conditions, indicate as more mobile trace elements in the lignite the elements As, B, Mn, Sr, in the fly ash the elements Cr, Li, Mo and Sr, and in the bottom ash the elements Li, Mo, Sr. In order to determine the geochemical affinity and the mode of occurrence of trace elements in the samples of lignite and its combustion by-products and to describe their behavior during the leaching at different pH conditions, a statistical process of the elemental analysis results is performed. In particular, the methodology of factor analysis R-type is used in the elemental analysis results, in the leaching values of trace elements of all samples, separately for pH 5 and pH 8,5 and in the fly ash and the bottom ash minerals.

O objetivo primário deste estudo é aprimorar o conhecimento acerca das fontes do manto e dos mecanismos envolvidos na gênese dos basaltos da Província Magmática do Paraná, que constitui uma das maiores manifestações de basaltos continentais do mundo. Para tanto, foram determinadas as concentrações de terras raras (La, Ce, Nd, Sm, Eu, Tb, Yb e Lu), outros elementos traço (Cs, Rb, Ba, U, Th, Ta, Hf, Co e Sc) e elementos altamente siderófilos (Os, Ir, Ru, Pt, Pd e Re), juntamente com razões isotópicas dos sistemas Rb-Sr, Sm-Nd, U-Th-Pb e Re-Os em basaltos com alto-Ti (Paranapanema e Pitanga) que ocorrem no norte da PMP. Além disso, foram determinadas as concentrações de elementos altamente siderófilos e as razões isotópicas de 187Os/188Os amostras representativas de basaltos com baixo-Ti (Esmeralda) do sul da PMP. Os dados geoquímicos e as razões isotópicas de Sr, Nd e Pb obtidos são consistentes com dados da literatura, porém, refinam as variações (extremos) isotópicas dos magmas-tipo Paranapanema e Pitanga. Esses dados, juntamente com as concentrações de elementos altamente siderófilos e das razões isotópicas de Os, inéditas na literatura, sugerem que as fontes dos basaltos (astenosfera ou manto litosférico subcontinental) sofreram metassomatismo significativo, com a intrusão de veios piroxeníticos, relacionado a antigas subducções e/ou processos de delaminação. / The primary goal of this study is to improve the understanding about the mantle sources and the mechanisms involved in the basalt genesis from Paraná Magmatic Province (PMP), which is one of the largest known continental flood basalts of the world. Therefore, the concentrations of rare earths (La, Ce, Nd, Sm, Eu, Tb, Yb and Lu), other trace elements (Cs, Rb, Ba, U, Th, Ta, Hf, Co and Sc) and highly siderophile elements (Os, Ir, Ru, Pt, Pd and Re) were determined, along with isotope ratios regarding Rb-Sr, Sm-Nd, U-Th-Pb e Re-Os systematics in high-Ti basalts (Paranapanema and Pitanga) from northern PMP. In addition, the highly siderophile element concentrations, as well as 187Os/188Os isotope ratios, were measured in selected samples of low-Ti basalts (Esmeralda) from southern PMP. The geochemical and Sr-Nd-Pb isotope results of the present study are consistent with literature data, but refine the isotope variations (extreme) for the Paranapanema and Pitanga magma-types. These data, along with the concentrations of highly siderophile elements and Os isotope ratios suggest that the basalt mantle sources (asthenosphere or subcontinental lithospheric mantle) were affected by significant metasomatism (piroxenitic vein hybridization), related with old subduction and/or delamination processes.

Thesis (MSc)--Stellenbosch University, 1964. / ENGLISH ABSTRACT: The influence of manganese sulphate sprays on the yield and ripening of fruit of manganese-deficient Vitis vinifera L. (cv. Pinotage) plants was investigated. Ripening was determined in terms of changes in concentration of the indivi= dual and total sugars and organic acids. Increasing concentrations of manganese sulphate resulted in significant increases in the manganese content of the leaves. The higher levels of manganese were associated with an increase in yield. Ripening, however, was retarded, in that the percentage sugar of the fruit was decreased and titrable acid content increased. The principal sugars present in the fruit were sucrose, glucose, fructose and xylose. Malic and tartaric acids were the main organic acid constituents. Glucose and fructose increased sharply, and sucrose and xylose slightly during ripening of the fruit, whereas malic and tartaric acid de= creased. Glucose, fructose, tartaric and malic acid tended to increase with increasing manganese content. Sucrose and xylose were not appreciably affected. An application of 1% manganese sulphate can be recommend- · ed for manganese deficient vineyards, as it results in an increased yield, in addition to delaying ripening until a more favourable time for handling. Furthermore, the lowered sugar content of the fruit may be advantageous for the pro= duction of dry wines from Pinotage grapes . / AFRIKAANSE OPSOMMING: Die invloed van mangaansulfaatbespuiting op die opbrengs en vrugrypwording van Vitis vinifera L. cv. Pinotage, wat aan ernstige mangaantekorte gely het, is ondersoek. Rypwording is met betrekking tot veranderings in die konsentrasies van totale en indiwiduele suikers en sure bepaal. 2. Toenemende konsentrasies Mnso4 (van O.2% tot l.O%) het n betekenisvolle toename in die mangaangehalte van die blare (van 3 tot 80 d.p.m.) tot gevolg gehad. Die ver= hoogde mangaangehalte het gepaard gegaan met n toe= name in opbrengs, terwyl rypwording vertraag is, deurdat die suikerpersentasie en die titreerbare suurgehalte ver= meerder is in vergelyking met die kontroleplante. 3. Die vernaamste suikers in die vrugte was sukrose, glukose, fruktose en xilose. Glukose en fruktose het vinnig en sukrose en xilose geleidelik toegeneem met die verloop van rypwording. In die ryp vrugte was glukose en fruk= tose oorheersend. Glukose en fruktose was geneig om toe te neem met toenemende mangaangehalte, terwyl sukrose en xilose nie beinvloed is nie. 4. Appelsuur en Wynsteensuur was die oorwegende sure in die vrugte. Beide hierdie sure het gedurende rypwording verminder. Hulle konsentrasies het oor die algemeen toegeneem namate die mangaankonsentrasie verhoog is. 5. Dit is afgelei dat bespuiting met 1.0% MnS04 aanbeveel kan word vir wingerde met mangaantekorte, daar dit n toename in opbrengs, gepaard met 'n vertraging in rypwording tot gevolg gehad het. So 'n vertraging mag moontlik in parstyd voordelig wees. Die verlaagde suikerpersentasie van die vrugte is moontlik gunstig vir die bereiding van droe wyne, waarvoor Pinotage hoofsaaklik gebruik word.

Σκοπός της παρούσας εργασίας, είναι η διερεύνηση των υδροχημικών παραμέτρων των κοκκωδών υδροφόρων της λεκάνης του Σπερχειού, καθώς και η πιθανή τροφοδοσία τους από τα ανθρακικά πετρώματα. Για το σκοπό αυτό πραγματοποιήθηκαν μετρήσεις στάθμης, καθώς και υδροχημικές αναλύσεις κύριων στοιχείων, ιχνοστοιχείων και σπάνιων γαιών. Γεωλογικά η περιοχή, στο βορειοανατολικό και νοτιοανατολικό τμήμα της ,δομείται από τους σχηματισμούς της Υποπελαγονικής ζώνης, στο νότιο από τους σχηματισμούς της ζώνης Παρνασσού-Γκιώνας και στο δυτικό από τους σχηματισμούς της ζώνης της Πίνδου. Οι Ολοκαινικές και Πλειο-πλειστοκαινικές αποθέσεις, δομούν το πεδινό τμήμα της λεκάνης και φιλοξενούν τον κύριο υδροφόρο ορίζοντα της περιοχής. Ο ελεύθερος αυτός υδροφόρος μεταπίπτει σε υπό πίεση, εξαιτίας της παρουσίας αργιλικών σχηματισμών, στα ανατολικά της περιοχής. Στα ορεινά τμήματα της λεκάνης, εντός των ανθρακικών σχηματισμών, αναπτύσσονται σημαντικοί υδροφόροι ορίζοντες. Με βάση τον πιεζομετρικό χάρτη της περιοχής προκύπτει ότι η διεύθυνση της ροής του υπόγειου νερού, είναι κυρίως ΒΑ-ΝΑ και o προσχωματικός υδροφόρος, τροφοδοτείται πλευρικά, από τους ανθρακικούς σχηματισμούς, που βρίσκονται νότια και βορειοανατολικά του πεδινού τμήματος. Τα υπόγεια νερά της περιοχής, ομαδοποιούνται σε τρεις κύριους υδροχημικούς τύπους: Ca-HCO3, Ca-Mg-HCO3 και (Ca)-Νa-Cl-(HCO3). Ο πρώτος υδροχημικός τύπος χαρακτηρίζει τα φρέσκα νερά της περιοχής, ο δεύτερος τα νερά που παρέμειναν για μεγαλύτερο χρονικό διάστημα στον υδροφόρο και εμπλουτίστηκαν σε Μg+2, και ο τρίτος τα νερά που δέχονται την επίδραση είτε της θάλασσας, είτε των θερμών νερών από μεγαλύτερα βάθη. Από τα αποτελέσματα των υδροχημικών αναλύσεων προέκυψε ότι στην πλειοψηφία τους τα δείγματα είναι κορεσμένα σε ασβεστίτη και δολομίτη. Eπίσης σε μία ομάδα δειγμάτων, διαπιστώθηκε απεμπλουτισμός σε Na, γεγονός που αποδόθηκε σε διαδικασίες ιοντοανταλαγής. Οι αυξημένες συγκεντρώσεις Fe, Mn, αποδόθηκαν στη διάλυση των ορυκτών του φλύσχη της Πίνδου, ενώ ο Zn και τα NΟ3 σε ανθρωπογενείς παρεμβάσεις (βιομηχανικά απόβλητα και λιπάσματα). Το As το Li και το Β συνδέονται με την παρουσία θερμών πηγών. Τέλος η μεθοδολογία των σπάνιων γαιών, επαλήθευσε τα αποτελέσματα της πιεζομετρίας αλλά και τα υδροχημικών αναλύσεων, ότι δηλαδή ο προσχωματικός υδροφόρος της περιοχής, τροφοδοτείται πλευρικά από τα ανθρακικά πετρώματα της περιοχής και συγκεκριμένα από τους ασβεστόλιθους της Υποπελαγονικής ζώνης και της ζώνης Παρνασσού-Γκιώνας. / In the frames of this study the hydrochemical parameters of porous aquifers at Sperchios basin, were investigated. Moreover their possible recharge by carbonate rocks was examined. Therefore, a series of water level measurements and a sampling campaign were carried out. The samples were analysed for main, trace and rare earth elements. Regarding the area’s geological setting, its northeastern and southeastern part is comprised of formations of the Subpelagonic Zone, its southern edge of Parnassos-Giona Zone and its western part of Pindos Zone. At the lowlands these formations are overlain by Holocene and Pleistocene deposits which host the most important aquifer of the region. It is an unconfined aquifer, which at the eastern part turns into a confined one, due to the presence of clay formations. Many important aquifers have been also developed in the basin’s carbonate formations. The region’s piezometric map at the southern area indicates that the main water flow direction is NE-SE. Moreover it points out that the carbonate formations recharge the porous aquifer. According to their hydrochemical characteristics groundwater can be divided into three main types: Ca-HCO3, Ca-Mg-HCO3 and (Ca)-Na-Cl-(HCO3). The first one is typical of the region’s fresh water, the second one indicates longer residence time of the water that was enriched in Mg+2 and the third one of water that was either influenced by sea water or hot springs. The elaboration of the hydrochemical data also showed that the majority of water samples are saturated in calcite and dolomite. There is also a depletion of certain samples in Na+ which was attributed to ion exchange processes. High Fe and Mn concentrations originate from the dissolution of Pindos Flysch minerals, As, Li and B to the presence of hot springs, while Zn and NO3 were related to human impact (industrial waste and fertilizers). The rare earth elements confirmed the original hypothesis, which was based on piezometric data and hydrochemical data analysis, that the region’s porous aquifer is laterally recharged by the carbonate rock formations of Subpelagonic and Parnassos-Giona Zone limestones.