The major constraints to food production in West Africa are related to the lack of suitable lands. Consequently, farmers incorporate organic amendments and wastewater to improve their yields. Within some limits, such wastes enhance soil fertility and can improve its physical properties. However, the advantages of using organic waste as fertilizer and soil amendment should be assessed with possible environmental and toxicological impacts due to the potential presence of heavy metals. The objective of this study was to assess the effect of organic amendments on heavy metal distribution in soils and vegetables in market gardens in Senegal. Organic amendments and soils samples were collected from four sites in eastern and southern Senegal. Samples were analyzed for physicochemical properties including particle size, total heavy metals, carbon content, nutrients, and pH. A sequential extraction procedure was conducted to determine heavy metal sinks. Results showed that sites were sandy in nature, low to medium in organic carbon content (8300 to 36600 mg kg-1), and had pH ranging from 5 to 7.9. The sequential extraction procedure showed that metals were distributed in the more stable soil fractions: Fe-Mn oxide, organic and residual. The highest soil metal concentrations in soils were found in Pikine and Rufisque sites. Plant samples were collected from these two sites and analyzed for total metal content. Results showed that all metal concentrations in soils, organic amendments, and vegetables were within the safe limits proposed by the World Health Organization, with the exception of Cd, Pb and Zn levels in vegetables. / Master of Science / Application of composted organic wastes and untreated wastewater to urban vegetable garden soils is raising serious concerns about possible health risks associated with the consumption of these vegetables particularly with regard to the concentrations of heavy metals in their edible portions. Therefore, this study focused on the evaluation of heavy metal concentrations in soils, organic amendments and vegetables from local gardens of Senegal and also, the determination of metal sinks in soil phases via a sequential extraction procedure (SEP). Soils, organic matter and vegetable concentrations of cadmium, cobalt, chromium, copper, manganese, nickel, lead and zinc were analyzed for total metals. Results from the SEP showed that metals in soils were located on the stable soil phases and would not be easily released unless environmental conditions changed (e.g. more acidic pH or anoxic conditions). Data from total metal analyses revealed that all metal concentrations in soil, organic amendments, and vegetables were within the safe limits proposed by the World Health Organization (WHO) with the exception of Cd, Pb and Zn levels in vegetables.

In the western United States, elevated selenium (Se) levels in soil have resulted in documented cases of ruminant fatalities. This is due to the ingestion of Se-hyperaccumulating vegetation growing on previously reclaimed phosphate mine soils. A field-scale analysis was first conducted to examine Se bioavailability to plants. Soil and plant samples were collected from transects from five study locations in Soda Springs, Idaho. Soils were analyzed for Se speciation and geochemical phases using a sequential extraction procedure (SEP). Additionally, speciation, SEP results, and Se bioavailability in the hyperaccumulator, western aster (Symphyotrichum ascendens (Lindl.)), were related using simple linear regression. Soil speciation and the validity of this SEP were then evaluated using synchrotron-sourced X-ray absorption fine structure (XAFS) spectroscopy for both whole and a sequence of extracted soils. Lastly, competitive adsorption of Se with two dissolved organic carbon (DOC) species, citric and salicylic acid, was examined on an amorphous iron oxide mineral surface. A strong relationship was identified for western aster Se and the first two combined SEP fractions, water-soluble and PO43--extractable Se (R2 = 0.85; P = <0.0001). Results also indicated a strong relationship between selenate and water-soluble Se (R2 = 0.83; P = 0.0002). This suggests that water extracts could be useful Se bioavailability assessment tools in highly contaminated systems. XAFS analyses indicated that elemental and organic Se were the most predominant phases overall in whole soils. The dominant oxidized species present was selenite sorbed onto iron oxides and calcite. Critical SEP evaluations using XAFS also indicate that oxidized Se species were underestimated by the SEP and elemental Se was overestimated. In extracted soils, XAFS results indicated partial recovery of carbonate, iron oxide and organic Se occurred. Therefore, it is suggested that researchers exert caution when employing SEPs. Additionally, sorption analyses demonstrated the highly competitive behavior of citric acid with both selenite (pH 5-8) and selenate (pH 5-6). Little competition was observed in the presence of salicylic acid for both Se species. Competition and subsequent desorption of both sorbed species in the presence of citric acid suggest a possible mechanism for Se solubilization and bioavailability in seleniferous environments. / Ph. D. / Selenium (Se) is a contaminant found in elevated levels in soils and plants in the Western United States due to phosphate mining. This has caused livestock deaths throughout the mining region following ingestion of plants with particularly high Se levels. Soils and plants were sampled from five study locations and used to assess relationships between soils and plant Se uptake. A sequential extraction procedure (SEP) was used to estimate Se in soils related to soluble, exchangeable, bound, organic, and elemental forms of Se. X-ray absorption fine structure (XAFS) spectroscopy was then used to critically evaluate the validity of these phases and the procedure accuracy. Lastly, the competitive effects of organic acids, which are naturally present in soils, on Se sorption was evaluated in a batch reactor system. From the SEP analysis, higher levels of Se were found in organic and elemental fractions, moderate quantities were observed in sorbed fractions, and smaller abundances were observed in soluble and exchangeable fractions. Relationships between soluble Se and selenate, a highly bioavailable form of Se determined from speciation analyses, indicated that simple water extracts could be used to assess Se “hotspots” in order to prevent further livestock fatalities. The critical evaluation of this SEP using XAFS determined that this procedure was under- and over-estimating bound and organic extracted phases of Se. This was possibly due to mineral and organics that were incompletely dissolved during extraction. It was determined that researchers should exert caution prior to using SEPs and have suggested several recommendations. Lastly, the batch reactor analysis indicated a form of DOC, citric acid, was highly competitive for mineral surface sites with selenite and selenate. Competition from salicylic acid was not obvious. Differences in competition were speculated to be linked to differences in molecular structure. This work suggests possible mechanisms for solubilization of both selenite, which is typically strongly bound, and selenate, which is typically soluble, in soil systems. Results offer an explanation for the exceedingly bioavailable nature of Se in the Western US.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23495号 / 工博第4907号 / 新制||工||1767(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 米田 稔, 教授 清水 芳久, 教授 高岡 昌輝 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

Το λιμάνι του Πειραιά είναι το πιο σημαντικό της Ελλάδας και ένα από τα σπουδαιότερα της Μεσογείου. Στην ευρύτερη περιοχή του λιμανιού λαμβάνουν χώρα ένα πλήθος από δραστηριότητες που επιβαρύνουν σημαντικά το λιμάνι σε βαρέα μέταλλα. Σκοπός της εργασίας αυτής είναι ο προσδιορισμός βαρέων μετάλλων σε επιφανειακά ιζήματα από το επιβατικό τμήμα του λιμανιού του Πειραιά. Στην αρχή γίνεται μια εισαγωγή για τα βαρέα μέταλλα και το ρόλο τους στα θαλάσσια ιζήματα. Ακολουθεί βιβλιογραφική ανασκόπηση που σχετίζεται με την παρουσία βαρέων μετάλλων σε θαλάσσια ιζήματα που έχουν συλλεχθεί από διάφορα λιμάνια με ποικίλες δραστηριότητες ανά τον κόσμο. Μετά από κάποια γενικά στοιχεία για το λιμάνι του Πειραιά, αναφέρονται στοιχεία της γεωλογίας της περιοχής μελέτης. Στην συνέχεια ακολουθεί περιγραφή των εργασιών πεδίου και γίνεται εκτενής αναφορά στην μεθοδολογία των χημικών αναλύσεων που εφαρμόστηκαν. Στους πυρήνες που συλλέχθηκαν έγιναν κοκκομετρικές αναλύσεις, προσδιορισμός οργανικού άνθρακα και προσδιορισμός συγκεντρώσεων βαρέων μετάλλων. Χρησιμοποιήθηκε η ολική διάσπαση (HF - HNO3 - HClO4) για τον προσδιορισμό των ολικών συγκεντρώσεων των μετάλλων και επίσης χρησιμοποιήθηκε η διαδοχική εκχύλιση για τον προσδιορισμό της χημικής κατανομής των μετάλλων στις διάφορες φάσεις των ιζημάτων και για την αποτίμηση της κινητικότητας τους. Τα αποτελέσματα των παραπάνω αναλύσεων έδειξαν την αρκετά σημαντική επιβάρυνση του λιμανιού σε βαρέα μέταλλα και προσδιόρισαν την κινητικότητα συγκεκριμένων μετάλλων. / The Port of Piraeus is the most important port in Greece as well as one of the important ports around the Mediterranean Sea. A lot of activities (commercial, industrial et.c) load the given port with a huge variety of heavy metals. The aim of this study is to determine the heavy metals in surface sediments from the passenger part of Port of Piraeus. At the beginning of the study there is an introduction of heavy metals and their role in marine sediments. A bibliographical review follows which is relevant to the presence of heavy metals found in marine sediments which have been collected from several ports around the world with various activities. Some data about the port is given, and then, takes place references for the geology of study area. Then, a description of field works and a detailed report of the methodology used for chemicals analysis follow. In the cores that were sampled, have been applied, grain size distribution and concentrations of heavy metals and organic carbon. In order to determine the total metal concentrations, the total digestion (HF-HNO3-HClO4) was used, and the sequential extraction procedure (BCR-SEP) was used for the determination of chemical speciation of metals. The results showed the enormous encumberment of port by heavy metals and determined the mobility of various metals.