The ecotoxicological literature reveals that countless researchers worldwide rely upon informally identified commercial earthworm stocks for laboratory bioassays. The primary aim of this study was to investigate laboratory and commercial stocks of Eisenia species used in South Africa in order to confirm their taxonomy, assess their levels of genetic richness and differentiation. To do so, populations of potential Eisenia andrei and Eisenia fetida were purchased/obtained from vermiculturists and laboratories from four provinces of South Africa. DNA barcoding was used to investigate these taxonomic uncertainties. The COI gene was partially amplified and sequenced in selected earthworms from eight local populations (focal groups) and two European laboratory stocks (non-focal groups). Only nine COI haplotypes were identified from the 224 sequences generated. One of these haplotypes was found to belong to the Megascolecidae Perionyx excavatus. The remaining eight haplotypes belonged to the genus Eisenia although only a single Eisenia fetida haplotype, represented by six specimens, was found in one of the European populations. The other seven haplotypes, all occurring in South Africa, were Eisenia andrei. No Eisenia fetida was found in the South African based populations. One of the commercial stocks from South Africa and a laboratory culture from Europe were mixes of E. andrei - P. excavatus and E. andrei – E. fetida respectively. COI haplotype numbers were limited to two to three distinct sequences within each of the local groups. This translated into a haplotype diversity (H) lower than 0.45 in all the populations, which is very low when compared to other such earthworm studies in which COI polymorphism has been investigated. Of all the local populations investigated, only the lone field population included was genetically divergent from the other populations. This was explained by the haplotype distribution across the populations which indicated that this population was the only one not harbouring the haplotype which represented 75% or more of the COI sequences within the local populations. Because research suggests that earthworm populations with limited genetic diversity may suffer inbreeding depression which could affect traits such as reproduction and survival, the secondary aim was to test whether metal-sensitive earthworms were overly present in the populations investigated. To do so, the three most common COI haplotypes identified between the 8 local populations of E. andrei (called Hap1, Hap2 and Hap3) were paired up and exposed to cadmium. A total of six couples were exposed to 0, 25, 50 and 100 mg Cd/kg for 4 weeks at 20ºC. The survival, biomass variation, cocoon production and cocoon hatching success were assessed for all the couples. The results indicated that couple 6 (Hap3xHap3) was the most sensitive for three of the endpoints assessed whereas couple 4 (Hap1 x Hap3) was the least sensitive. Cocoon hatching success could not help differentiate the couples. The analysis of Cd tissue contents revealed that with increasing Cd concentration, Cp6 (Hap3xHap3) could accumulate significantly more Cd than any other couple (p ≤ 0.01). These findings indicate that earthworm populations may carry intrinsically metal-tolerant and metal-sensitive genotypes. In the context of ecotoxicological testing, the present results underline the importance of using genetically diverse populations in laboratory testing as Cp6 (Hap3xHap3) could have suffered from the deleterious effect of inbreeding. Because E. fetida could not be found in the local populations assessed, it is recommended that further earthworm DNA barcoding studies, covering a more representative geographical area of South Africa and including more field populations of Eisenia spp. be conducted. Because of the occurrence of genetic homogeneity in the populations studied, it is suggested that captive breeding initiatives be established using specimens obtained from several geographically distant field and reared populations. Further research investigating patterns of Cd accumulation/excretion kinetics between the Cd-tolerant and Cd-sensitive individuals reported in the present study, should be conducted to help determine whether inbreeding is the sole factor explaining the observed genotypic responses to Cd. Finally, the necessity of a standardised earthworm barcoding protocol that could help both to properly identify laboratory earthworm stocks and to select genetically diverse stocks suitable for laboratory testing, is discussed together with the relevance of the present work to ecotoxicological testing in general. / MSc (Environmental Sciences), North-West University, Potchefstroom Campus, 2015

Doctor of Philosophy / Department of Mechanical and Nuclear Engineering / Douglas S. McGregor / Cadmium Zinc Telluride (CdZnTe) has been used for many applications, such as medical imaging and astrophysics, since its first demonstration as a room temperature operating gamma-ray detector in 1992. The wide band gap, high effective Z-number and high resistivity of CdZnTe make it a good candidate for use as a room temperature operated detector with good absorption efficiency, while maintaining a low bulk leakage current at high electric fields. Nevertheless, the low mobility lifetime products mu tau of holes in CdZnTe makes detectors position sensitive, unless advanced detector designs are employed. Among those designs is the Frisch collar technology which turns the detector into a single carrier device by negating the degrading effects of hole trapping and low mobility. The superiority of the Frisch collar technology over other methods include its inexpensive associated electronics and straight forward fabrication process. The main objective of this research study is to develop a large volume gamma-ray detector with an array of individual CdZnTe Frisch collar gamma-ray spectrometers while still using a single readout. Several goals were to be accomplished prior to the main objective. One goal is to develop a reliable low cost method to fabricate bulk CdZnTe crystals into Frisch collar detectors. Another goal was to investigate the limitations of crystal geometry and the crystal electrical properties to obtain the best spectroscopic performance from CdZnTe Frisch collar detectors. Still another goal was to study all other external parameters such as the collar length, anode to cathode ratio, the insulator thickness and applied voltage on performance of CdZnTe Frisch collar detectors. The final goal was to construct the CdZnTe Frisch collar devices into an array and to show its feasibility of being used for large volume detector.

The Mae Tao watershed, northwestern Thailand, has become contaminated with cadmium (Cd) from the zinc mining activities area in the nearby Thanon-Thongchai mountains. Consumption of Cd-contaminated rice has led to documented human health impacts. The aim of this study was to clarify transfer pathways from creek and canal waters to the paddy field soils near Baan Mae Tao Mai village and to determine the relationship between Cd forms in the soil and uptake by rice plants. Soils, irrigation canal sediments and water samples were collected during the dry season and at the onset of the rainy season. Rice samples were collected at harvesting time and samples of soil fertiliser were also obtained. Water samples were filtered, ultrafiltered and analysed by ICP-MS whilst sub-samples of dried, ground soils and sediments were first subjected to micro-wave assisted acid digestion (modified US EPA method 3052). XPRD and SEM-EDX methods were used for mineralogical characterisation and selective chemical extractions have assisted in the characterisation of solid phase Cd associations. Transfer mainly occurred in association with particulate matter during flooding and channel dredging and, in contrast with many other studies, most of the soil Cd was associated with exchangeable and carbonate-bound fractions. Moreover, there was a significant positive relationship between soil total Cd and rice grain Cd (R2=0.715), but a stronger relationship between both the Tessier-exchangeable soil Cd and the BCR-exchangeable soil Cd and rice grain Cd (R2=0.895 and 0.861, respectively). Stable Isotope Exchange (gives isotopically exchangeable Cd - E value) is generally considered to provide a better measure of bioavailability. The results of this study showed that SIE gave values which significantly positive correlated with the Tessier exchangeable fraction. Biochar has a porous structure and acidic functional groups on its surface which give it a high capacity to affect heavy metal adsorption when added to soils. Biochar samples were produced from rice husk (RHC) and miscanthus (MC) since these are cheap and readily available materials in Thailand. Indeed rice husk char is already used for rice seed germination by local farmers. Evaluation of the chemical and physical properties of the chars showed that the lower temperature (350°C) chars had greater proportions of oxygen-containing functional groups than those produced at 700°C. Moreover the low temperature RHC had the greater cation exchange capacity than the MC produced at the same temperature. In abiotic feasibility tests, it was shown that RHC was more effective than MC at lowering soil available Cd. The former reduced the E values for the medium-Cd soils by 4.7% and 16.0% when 1% and 5% RHC, was added, respectively. From pot experiments, in medium-Cd soils, 1% and 5% RHC amendment showed the potential to decrease Cd uptake by rice roots. However, further work involving addition of a greater proportion of biochar with a higher number of replicates is needed to reach more robust conclusions.

Thesis (MSc)--University of Stellenbosch, 2006. / ENGLISH ABSTRACT: The development of potential genetically based resistance to cadmium (Cd) after long-term exposure to this metal at a sublethal concentration, was investigated in earthworm specimens belonging to the genus Eisenia. Adult (clitellate) earthworms from a long-term laboratory Cdexposed population (> 78 generations) and from other populations having no previous history of metal exposure were exposed to increasing concentrations (0; 2.5; 5; 10 and 20 mg/l) of Cd in the form of CdSO4. Different biomarkers and molecular markers were used to determine whether the specimens from the long-term Cd-exposed population had acclimatized or adapted to the metal contaminated environment. Acclimation was investigated at different physiological and biochemical levels using the following three biomarkers: the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide assay (MTT assay) measuring mitochondrial activity and cell viability; the single cell gel electrophoresis assay (comet assay) measuring DNA strand breaks and the biosynthesis of metallothioneins (MTs) that have the function of lowering metal toxicity. Earthworms from the long-term exposed substrate as well as specimens from populations not exposed to Cd were used. Adaptation was investigated by looking at both allozyme polymorphism at seven enzyme encoding loci and DNA polymorphism using chosen neutral and selectable genetic markers. The markers used were cytochrome c oxydase subunit I (COI) and metallothionein-2 (mt-2) respectively. This was done amongst the same pool of populations. Additionally, the DNA polymorphism study also aimed at genetically identifying the species utilized in this study thereby determining whether these earthworms belong to the species Eisenia fetida or Eisenia andrei. MTs biosynthesis did not generate the expected data mainly due to the fact that a suitable antibody could not be obtained (discussed in Chapter 5 section 5.3.3.). Similarly, the assessment of DNA polymorphism at the chosen selectable genetic marker mt-2 did provide information relevant to understanding the potential development of resistance to Cd in the long-term metal contaminated group. COI sequences generated in this study were compared to E. fetida and E. andrei COI sequences available on Genbank. Consequently, specimens used in this study were identified as possibly belonging to the species E. andrei. Allozyme polymorphism revealed no fixed genetic differences between the long-term Cd exposed laboratory culture and the rest of the populations. All the populations departed from Hardy-Weinberg equilibrium (χ2 > 5.9; p < 0.05), and showed a low mean heterozygosity per locus (Ho ≤ 0.21), probably due to inbreeding. Cell viability and proliferation as tested by the MTT assay revealed that coelomocytes, isolated from the long-term Cd-exposed group showed the highest viability (98.42%) compared to those from other groups (+/- 80%). Kruskal-Wallis ANOVA (H2, 225=109.7165 p < 0.001) revealed that the long-term Cd-exposed laboratory culture showed a better response to acute exposure to Cd, thus demonstrating that these worms have developed some kind of tolerance to Cd. Similarly, the comet assay showed that in the long-term Cd-exposed specimens, less DNA breaks occurred after Cd exposure than in the unexposed groups. Of all the comet parameters assessed in this study (comet tail length, tail moment and tail DNA percentage), tail DNA percentage seemed to be more sensitive although all three parameters indicated that long-term Cd-exposed specimens were more resistant than unexposed specimens as shown by the number of single strand DNA breaks induced by exposure to higher concentrations of Cd (p < 0.001). The comet and the MTT assays indicated that the earthworms with a previous history of Cd exposure have developed increased fitness towards higher doses of Cd, compared to previously unexposed groups. These findings mainly proved that several mechanisms could come into play at the physiological and biochemical level to allow the Cd exposed population to acclimatize to its chemically stressful environment. Clear genetic support for the differences found between the tested populations was not obtained, but needs to be investigated further using Cd selectable markers such as the mt-2 gene, in order to come to a more conclusive deduction. / AFRIKAANSE OPSOMMING: Die moontlike ontwikkeling van geneties gebaseerde weerstand teen kadmium (Cd) by erdwurms van die genus Eisenia, na langtermyn blootstelling aan die metaal by 'n subletale konsentrasie, is ondersoek. Volwasse (klitellate) erdwurms van 'n langtermyn laboratorium Cdblootgestelde bevolking (< 78 generasies) asook van ander bevolkings met geen voorgeskiedenis van metaal blootstelling nie, is blootgestel aan 'n reeks van Cd konsentrasies (0; 2.5; 5; 10; en 20 mg/l) in die vorm van CdSO4. Verskillende biomerkers en molekulêre merkers is gebruik om vas te stel of die erdwurms geakklimeer of aangepas het by die metaal in die gekontamineerde omgewing. Akklimasie is op verskillende fisiologiese en biochemiese vlakke getoets deur die volgende drie biomerkers te gebruik: Die 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromied toets (MTT toets), wat mitochondriale aktiwiteit en sel lewensvatbaarheid meet; die enkel sel elektroforese toets (Komeettoets) wat DNS string breuke meet; die biosintese van metallotioniene (MT's) wat metaalvergiftiging verlaag. Erdwurms van die langtermyn blootstellingsubstraat asook eksemplare van bevolkings wat nie aan kadmium blootgestel was nie, is gebruik. Aanpassing is ondersoek deur gebruik te maak van allosiem polimorfisme, waar 7 ensiem koderende lokusse gebruik is asook van DNS polimorfisme deur neutrale genetiese merkers te selekteer. Die merkers wat gebruik is, was sitochroom c oksidase, subeenheid I (COI) en metallotionien-2 (mt-2) respektiwelik. Hierdie toetse is met dieselfde groepe bevolkings uitgevoer. 'n Bykomende van die studie aspek waar ook van DNS polimorfisme gebruik gemaak is, was daarop gemik om die spesie wat vir die huidige studie gebruik is, geneties te identifiseer en om vas te stel of die erdwurms aan die spesie Eisenia fetida of Eisenia andrei behoort. Die MT biosintese het nie die verwagte data gegenereer nie, hoofsaaklik weens die feit dat geskikte teenligaampies nie beskikbaar was nie (bespreek in Hoofstuk 5 afdeling 5.3.3). Soortgelyk, het die waardebepaling van DNS polimorfisme by die geselekteerde genetiese merker mt-2 nie genoegsame informasie verskaf om die potensiaal van die ontwikkeling van weerstand teen Cd in die langtermyn blootgestelde groep te verstaan nie. COI geenvolgordes van E. fetida en E. andrei wat op Genbank beskikbaar was, is gebruik om met die resultate van die huidige studie te vergelyk. Die spesie wat tydens die huidige studie gebruik is, is op hierdie wyse geïdentifiseer as E. andrei. Allosiem polimorfisme het geen vaste genetiese verskille tussen die langtermyn blootgestelde laboratoriumkulture en die ander bevolkings getoon nie. Al die bevolkings het verskil van die Hardy-Weinberg ewewigstoestand (χ2 > 5.9; p < 0.05) en het 'n lae heterosigositeit per lokus getoon (Ho ≤ 0.21), moontlik as gevolg van inteling. Sellewensvatbaarheid en proliferasie soos getoets met die MTT toets, het getoon dat selomosiete, geïsoleer vanuit die langtermyn Cd blootgestelde groep, die hoogste lewensvatbaarheid (98.42%) gehad het in vergelyking met die ander groepe (+/- 80%). Kruksal-Wallis ANOVA (H2, 225=109.7165 p < 0.001) het getoon dat die langtermyn Cd blootgestelde laboratoriumkultuur 'n beter respons vir akute blootstelling aan Cd gehad het. Hierdeur is gedemonstreer dat hierdie wurms 'n soort toleransie teenoor kadmium ontwikkel het. Soortgelyk het die komeettoets aangetoon dat daar in die langtermyn blootgestelde eksemplare minder DNS breuke voorgekom het na verdere blootstelling aan Cd as in die ander groepe. Van al die komeet parameters wat tydens die studie gemeet is (komeet stertlengte, Olive stert moment en stert DNS persentasie), het die stert DNS persentasie geblyk om die mees sensitiefste te wees, alhoewel al drie parameters aangetoon het dat die langtermyn Cd blootgestelde eksemplare meer weerstandbiedend was teen induksie van DNS enkelstring breuke weens Cd blootstelling (p < 0.001), as die wat nie voorheen blootgestel was nie. Die komeet en MTT toetse het aangetoon dat erdwurms met 'n voorgeskiedenis van Cd blootstelling 'n toenemende fiksheid teen hoër dososse van Cd ontwikkel het as die wat nie voorheen aan kadmium blootgestel was nie. My bevindings kon hoofsaaklik toon dat verskeie meganismes op die fisiologiese en biochemiese vlak 'n rol sou kon speel om Cd blootgestelde bevolkings by 'n chemies stresvolle omgewing te laat akklimeer. Duidelike ondersteuning vir die verskille tussen die getoetsde bevolkings deur van Cd geselekteerde merkers soos die mt-2 geen gebruik te maak om 'n meer finale afleiding te kan maak is nie verkry nie en behoort verder ondersoek te word.

Thesis (PhD)--Stellenbosch University, 2002. / ENGLISH ABSTRACT: Metals occur naturally in the environment but since the industrial revolution the amounts ofbioavailable metals in the environment have increased significantly. There are various anthropogenic sources of metals in the environment. In recent years there has been an increasing interest in the use of biomarkers in terrestrial invertebrates for the assessment of the potential adverse effects of chemicals in soil ecosystems. Terrestrial isopods are one of the groups that play an important role in the decomposition process as fragmentors of dead plant material in soil ecosystems. They are also known to accumulate contaminants in their bodies, especially in the hepatopancreas. Cadmium has no known biological function and is deposited in the environment through a variety of sources. Zinc on the other hand is one of the essential metals and play an important role in the normal metabolism of animals. Zinc too, is deposited in the environment through a variety of anthropogenic sources. The aim of this study was to undertake an experimental and field evaluation of the role cellular change in the hepatopancreas of terrestrial isopods can play in conjunction with other sublethal responses to contribute to the assessment of the impact of cadmium and zinc in terrestrial ecosystems. Porcel/io laevis was used as test species in the laboratory experiments in this study, to conduct sublethal toxicity tests. Cadmium- and zinc sulphate were used as the contaminants, applied separately and as mixtures. The isopods were weighed before the beginning of the exposures and every week throughout the exposure period of six weeks. At the end of the exposure period they were dissected to remove the hepatopancreas. The zinc and cadmium content of the hepatopancreases and rest of the bodies of the isopods were determined by atomic absorption spectrophotometry. Hepatopancreas samples were also prepared for histological analysis, and measurements of the Percentage Cellular Area (PCA) were made using image analysis. Specimens of Porcellionides pruinosus were collected from contaminated- and uncontaminated field sites. Hepatopancreas- and rest of the body samples of P. pruinosus were also analysed for cadmium and zinc. Histological sections of the hepatopancreas were similarly prepared and analysed, as in the laboratory experiments. Exposure to cadmium- and zinc sulphate affected the mass of P. laevis negatively in the single metal exposures. However, these two metals "neutralised" each other's effects in the mixture toxicity exposures, pointing towards an antagonistic interaction. Administered cadmium- and zinc sulphate resulted in the accumulation of cadmium and zinc in the isopods, especially in the hepatopancreas. In the mixture toxicity experiments cadmium and zinc influenced the accumulation of each other. Cadmium- and zinc sulphate, whether administered separately or as mixtures, changed the structure of the hepatopancreas and this was quantitatively shown through PCA measurements. PCA of the hepatopancreas of terrestrial isopods was shown to be a good general biomarker of exposure and effects for cadmium as well as for zinc. It is suggested that PCA could serve as a general biomarker to predict possible impairment of growth or mass change of isopods exposed to cadmium and zinc mixtures. The findings of the field survey also suggest that PCA may be suitable to be used as a general biomarker to measure metal induced stress in woodlice from contaminated field sites. / AFRIKAANSE OPSOMMING: Metale kom natuurlik voor in die omgewing, maar sedert die industriële revolusie het die hoeveelheid bio-beskikbare metale in die omgewing betekenisvol toegeneem. Daar is verskeie antropogeniese bronne van metale in die omgewing. Die afgelope paar jaar was daar toenemende belangstelling in die gebruik van biomerkers by terrestriële invertebrate vir die assessering van potensiële negatiewe effekte van chemiese stowwe in grondekosisteme. Terrestriële Isopoda is een van die groepe wat 'n belangrike rol speel III die ontbindingsproses as fragmenteerders van dooie plantmateriaal III grondekosisteme. Hulle akkumuleer ook kontaminante in hul liggame, veral in die hepatopankreas. Kadmium het geen biologiese funksie nie, en word vrygestel in die omgewing deur verskeie bronne. Sink, aan die ander kant, is een van die essensiële metale en speel 'n belangrike rol in die metabolisme van diere. Sink word ook in die omgewing vrygestel deur 'n verskeidenheid antropogeniese bronne. Die doel van die studie was om deur eksperimentele en veldondersoek die rol van sellulêre veranderinge in die hepatopankreas van terrestriële Isopoda in samehang met ander subietale response te evalueer om by te dra tot die assessering van die impak van kadmium en sink op terrestriële ekosisteme. Porcellio laevis is as toets-spesie in die laboratorium eksperimente gebruik om subietale toksisiteitstoetse mee uit te voer. Kadmium- en sinksulfaat is as kontaminante gebruik, en is apart en gemeng toegedien. Die houtluise is geweeg voor die begin van die blootstellings en elke week deur die loop van die blootstellingsperiode van ses weke. Aan die einde van die blootstellingsperiode is hulle gedissekteer om die hepatopankreas te verwyder. Die sink en kadmium inhoude van die hepatopankreas en res van die liggame van die houtluise is bepaal met behulp van atoomabsorpsiespektrofotometrie. Monsters van die hepatopankreas is ook voorberei vir histologiese analise, en metings van die Persentasie Sellulêre Oppervlak (PSO) is gedoen met behulp van beeldanalise. Eksemplare van Porcellionides pruinosus is versamel van 'n gekontamineerde- en 'n ongekontamineerde gebied. Monster van die hepatopankreas en res van die liggaam van P. pruinosus is ook geanaliseer vir kadmium en sink. Histologiese sneë van die hepatopankreas was ook voorberei en geanaliseer, soos in die laboratorium eksperimente. Blootstelling aan kadmium- en sinksulfaat het die massa van P. laevis negatief beïnvloed in die enkelmetaal-eksperimente. Hierdie twee metale het egter mekaar se effekte in die mengseltoksisiteitstoetse "geneutraliseer". Dit dui op 'n antagonistiese interaksie. Toegediende kadmium- en sinksulfaat het gelei tot die akkumulasie van kadmium en sink in the houtluise, veral in die hepatopankreas. In die mengseltoksisiteitstoetse het kadmium en sink mekaar se akkumulasie beïnvloed. Kadmium- en sinksulfaat, apart of as mengsels toegedien, het die struktuur van die hepatopankreas verander, en dit is kwantitatief aangetoon deur die PSO metings. PSO van die hepatopankreas van houtluise is 'n bruikbare algemene biomerker van blootstelling en effek vir kadmium en sink. Dit word voorgestel dat PSO kan dien as 'n algemene biomerker om negatiewe effekte op die groei of massaverandering van houtluise te voorspel wat aan kadmium en sink mengsels blootgestel word. Die bevindinge van die veldondersoek dui daarop dat PSO gepas mag wees om gebruik te word as 'n algemene biomerker om metaal-geïnduseerde stres by houtluise vanaf 'n gekontamineerde gebied te meet.

The exploitation of metallic sulfide ores produces vast quantities of fine-grained wastes hosting potentially toxic elements (PTEs). There are concerns that, if improperly disposed of and managed, waste mineral particles can behave as vectors that disperse PTEs via aeolian and fluvial transport, subsequently contaminating soils and crops used to support human populations. The importance of these particles, as sources and influencers of PTE biogeochemistry in productive soils, has received limited research. Long-term (365 d) batch incubation experiments, field weathering experiments and phytoavailability trials, were performed to establish the rate, patterns and factors limiting PTE (Cd, As, Hg) release from grains of sphalerite (Zn(Fe,Cd)S), arsenopyrite (FeAsS) and cinnabar (HgS) into soil matrices (0.1 % mineral:soil m/m), and the bioavailability of the liberated PTEs to important food crops (Tricitum aestivum, wheat and Oryza sativa, rice). All three of the ores underwent chemical weathering in oxic agricultural soils of both temperate and sub-tropical provenance, during which nonessential PTEs (cadmium, mercury, arsenic) were released in bioavailable forms, at rates relevant to agricultural production. Sphalerite weathered at a rate of 0.6 to 1.2 % a-1 (Cd basis) in the experimental soils, releasing 0.5 to 1 μmol Cd g-1 ZnS a-1 into the soil matrix. Cinnabar weathering reached a maximum of 12.0 – 13.5 % (Hg basis) after 90 days exposure in oxic soils, whereas arsenopyrite weathering was rapid and extensive, reaching 56 to 66 % (S basis) after 180 days. The PTE concentrations accumulated in edible grains of wheat and rice grown in the sulfide-contaminated soils were higher than international food safety limits by factors of 8 (Cd in rice), 10 – 30 (Hg in wheat and rice) and 8 – 12 (As in wheat and rice). The primary geochemical factors controlling PTE release and bioavailability were solid-phase associations (i.e. PTEs complexed by clays, metal oxyhydroxides and organic matter) and the precipitation of secondary mineral phases. Weathering arsenopyrite grains were passivated from further oxidation by secondary iron-arsenate phases, which also co-precipitated arsenic liberated from the ore. Secondary phase formation was identified as the cause of decreasing extractable Hg (liberated from cinnabar) after mercury release from cinnabar peaked (≤ 90 days exposure). For sphalerite, the evidence indicates that secondary sulfide phases formed under flooded (sulfate-reducing) soil conditions (paddy rice), limited the bioavailability of cadmium previously liberated under oxic conditions. These key findings demonstrate a potential human health hazard relating to the dispersal of PTE-hosting sulfide ore particles produced by mining activities into soils supporting human populations via crop contamination. This work also highlights differences in ore geochemistry, showing the need for additional research on different ore minerals and their alteration products.

No description available.

published_or_final_version / abstract / Anatomy / Doctoral / Doctor of Philosophy

Des plantules de fève (Vicia faba), âgées de 12 jours sont traitées en conditions hydroponiques par 50, 100 et 200 µM de chlorure de cadmium pendant 12, 24 et 48 h. Les signes d'intoxication se manifestent par des perturbations de la croissance foliaire et racinaire accompagnées d'un brunissement des racines traitées. Nos résultats ont aussi montré, une diminution de la teneur en chlorophylle totale, un désordre nutrititionnel et des perturbations de l'absorption de l'eau dans les plantules de fève traitées. Concernant la répartition de Cd entre les feuilles et les racines de fève, nous avons montré un faible passage des ions métalliques vers les feuilles et une localisation préférentielle de ces ions dans les racines. La présence des ions cadmiques dans la solution nutritive a entrainé l'installation d'un état de stress oxydant caractérisé par une production accentuée de O2- et de H2O2 dans les racines et les feuilles de plantules de fève traitées. Dans les racines, la production de radicaux d'oxygène actif s'accompagne d'une augmentation de la production de MDA (malondialdéhyde), une stimulation de l'activité lipoxygénasique (LOX) au début du traitement et un accroissement du taux de mort cellulaire. Dans les feuilles traitées par le cadmium, nous n'avons pas montré des modifications de la production de MDA par rapport aux témoins. Face au stress cadmique, les plantules de fève mobilisent des systèmes antioxydants pour éliminer les espèces réactives de l'oxygène (ROS). Nous avons noté des perturbations des activités des enzymes antioxydantes (SOD , CAT, GPX, et des enzymes du cycle ascorbate-glutathion), des modifications des rapports ASA/DHA et GSH/GSSG et une production accentuée des composés phénoliques. Dans les racines, organes qui accumulent le Cd, nous avons noté une augmentation de la teneur en phytochélatines et une modification de l'expression de certains gènes liès au stress métallique (hsp70.1, CuZnSODcy, GR). Dans les zones méristématiques de ces organes, nous avons montré aussi une baisse de l'indice mitotique, une induction des micronoyaux et l'apparition d'anomalies chromosomiques touchant la structure et le nombre des chromosomes.

Le lait peut être utilisé comme indicateur de pollutions environementales car en général on est assuré de la bonne tracabilité de sa collecte. De nombreux solvants ont été utilisés pour séparer les principales phases du lait (protéines, lipides, sérum). Le mélange de solvants utilisés pour cette étude est le suivant: 1 vol de lait, 1 vol de solution NaCL à 0.9%, 2 vol d'éthanaol et 4 vol de dichlorométhane......