There is increasing global recognition of the effects of large scale land disturbance by wildfire on a wide range of water and ecosystem services. In 2003, the Lost Creek wildfire burned a contiguous area of 21,000 ha on the eastern slopes of the Rocky Mountains in southern Alberta. This disturbance had a significant and prolonged impact on the water quantity and quality of downstream river reaches and reservoirs in the Oldman watershed. Previous research in this watershed demonstrates that dissolved metal concentrations in rivers draining burned landscapes were 2 to 15 times greater than in unburned reference streams (Silins et al. 2009a). Currently there is no information on the effects of wildfire on the bioaccumulation and toxicity of sediment-associated metals in fire-impacted streams in Alberta. This study was designed to evaluate the linear downstream disturbance effects of wildfire in the Crowsnest River located in southern Alberta. The toxicity and bioaccumulation of particulate-associated metals from wildfire impacted tributaries to the Crowsnest River on freshwater amphipod Hyalella azteca were evaluated. Phillips samplers were deployed to collect suspended solids in streams draining burned zone impacted by the Lost Creek wildfire and reference (unburned) zones within the area. Metal toxicity and bioaccumulation were determined in the laboratory by exposing the epi-benthic freshwater amphipod Hyalella azteca to particulates collected from the Crowsnest River. A metal effects addition model (MEAM) was used to assess the impact of metal mixtures and to predict chronic mortality (Norwood et al. 2013). Increased concentrations of Al, Ba, Co, Cr, Mn and Zn were found in the tissues of H. azteca exposed to particulates from burned watersheds in comparison to the unburned watersheds. H. azteca mean survival was similar when exposed to the particulates samples from both burned and unburned sites indicating that 9 years after this landscape disturbance, there was little impact due to the wildfire. However, at burned site (B1), the observed survival was lower than survival predicted by MEAM. The data suggests that factors other than the metals examined in this study were influencing the survival of H. azteca. The concentrations of sediment-associated metals have decreased in the nine years since the wildfire, and minimal metal toxicity was observed in H. azteca. Although metal toxicity in H. azteca was minimal 9 years after the Lost Creek Fire, the short term effects of wildfire on metal toxicity remain largely unknown. In addition, other factors such as burn severity, stream size and hydroclimatic conditions can influence the effects of wildfire on abundance and diversity of aquatic invertebrates (Minshall et al. 2001). Therefore, the influences of those factors on metal toxicity as a result of wildfire should be rigorously assessed in future studies.

Aluminium is the third most abundant element in the lithosphere and yet no biological function has been elucidated. The ubiquity and pH-dependent chemical speciation of aluminium provides multiple routes of exposure to organisms, inducing neurotoxicity, tissue necrosis and organelle dysfunction. However, many studies of aluminium toxicity lack consideration of the speciation and relevant concentration of aluminium and the route of exposure. The aim of this thesis was to examine the accumulation, distribution, excretion and toxicity of aluminium following a common route of exposure (ingestion) at a concentration likely to be encountered by the model organism (freshwater crayfish, Pacifastacus leniusculus) in the wild. Crayfish are sediment dwelling omnivorous crustaceans distributed worldwide and as such are vulnerable to multiple routes of aluminium exposure. They play a central role in aquatic food webs and are becoming increasingly popular for human consumption, raising concern about food chain transfer. Crayfish were fed aluminium chloride-spiked artificial food pellets for either 20 days, 28 days + 10 day aluminium-free clearance period, or 22 weeks + 4 week aluminium-free clearance period. In addition, systemic administration of aluminium citrate was undertaken to draw comparisons with previous mammalian work and compare the two routes of exposure. Tissue distribution and accumulation was measured in the gills, hepatopancreas, flexor muscle and antennal gland. Stress and tissue damage were analysed using biochemical and histopathological techniques. Behavioural toxicity tests and measurements of the neurophysiological parameters of the crayfish medial giant neuron were used to assess aluminium-induced neurotoxicity. In vitro neurotoxicity tests with aluminium chloride were also carried out on isolated nerve tissue to assess the suitability of in vitro studies. The key site of aluminium accumulation following ingestion was the hepatopancreas. Excretion was observed via the gills, antennal glands (in the urine) and hepatopancreas (for incorporation into the faeces). However, physiological consequences such as tissue damage, inflammation and altered neuronal activity were observed and persisted even after cessation of aluminium ingestion. Consequently there are implication for crayfish fitness and survival, the aquatic food web and human toxicity following ingestion of aluminium.

For decades, researchers have been working to better understand the effects of acid and metal toxicity to aquatic organisms and to develop ways to effectively mitigate these detrimental effects. Acid mine drainage (AMD) causes environmental pollution that affects many countries having historic or current mining industries. Both surface and underground mining have the potential to create AMD and therefore adversely affect the local and adjacent environments. Through malignant mining and farming practices, damming rivers and the changing climate, surface freshwater resources are rapidly being reduced in Australia. Mine pit lakes offer a large freshwater resource that if managed correctly may sustain significant environmental, social and economic benefits from selected end uses for the future. However, assessment of mine pit lakes needs to be achieved to validate end use options. The Collie Basin located in the southwest of Western Australia is a coal mining area with many abandoned open cast mines (OCM). Some of these OCM have filled with water forming mine pit lakes that are affected by AMD. The result is large freshwater bodies with moderate to high concentrations of metals and a low pH. High concentration of metals combined with low pH is of environmental concern to both the aquatic and terrestrial ecosystem. Nevertheless, remediation techniques for AMD are available and applicable to these acidic lakes. However, the lakes in the Collie Basin are low in sulphatic compounds, therefore, restricting the use of the most common remediation treatment of bioremediation with sulphate reducing bacteria. Three remediation treatments were assessed for there efficacy in toxicity amelioration to three mine pit lakes. The treatments assessed were Limestone addition, phosphorus addition and a Rapid Catalytic Oxidation (RCO) treatment. / Toxicity assessment was achieved by means of comparing physico-chemical data to guideline trigger values and biological assessment. Biological assessment was achieved with three commonly used but ecologically and geographically relevant species. The bioassay species were the alga Chlorella protothecoides, the crustacean Ceriodaphnia cf dubia and the protozoa Tetrahymena thermophila. Aquaculture is being trialled adjacent to one of the pit lakes in limestone treated mine pit lake water. Therefore, the aquaculture fish species Bidyanus bidyanus early life stages were also used to assess residual toxicity from treated mine pit lake water. Limestone remediation of pit lake water demonstrated good reduction of dissolved metal concentrations with the exception of Zn and the ability to increase pH to circum-neutral. Biological assessment of limestone treated pit lake water showed that toxicity was removed to the three bioassay species and to the aquaculture species B. bidyanus early life stages. A larger field- scale mesocosm experiment with limestone treatment in situ is recommended. Assessment of the mesocosm experiment with biological and chemical analysis will confirm the efficacy of this treatment for full scale use.

Metal toxicity is implicated in neurotoxicity, nephrotoxicity, aging and cancer. Protein oxidation resulting from oxidative stress is now known to be involved in metal toxicity. However, proteomic responses to metal induced oxidative stress have not been characterized. By using the yeast as a model, we characterized these changes occurring in response to sub-lethal doses of metals. Several proteins involved in protein synthesis, ribosome assembly decreased while antioxidant defenses, proteins involved in sulfur metabolism, and glutathione synthesis and ubiquitin increased following metal exposure. We also show that metals induced temporal and targeted protein oxidation independent of protein abundance. Among the targets were glycolytic enzymes and heat-shock proteins. As a consequence, glycolytic enzyme activities decreased whereas the levels and activities of the enzymes of the alternative pathway for glucose metabolism, pentose phosphate pathway (PPP) increased. True to prediction, we also found increased flow through the PPP as measured by elevated levels of NADPH and glutathione. NADPH and glutathione are crucial for maintaining the redox balance in the cell. Thus, rerouting of glucose metabolism into PPP is considered to be beneficial to the organism. Among the oxidation targets is a glycolytic protein, glyceraldehyde 3-phosphate dehydrogenase (GAPDH) that is required for apoptosis in neuronal cells. We show that not only is GAPDH required for metal induced apoptosis in yeast but also the levels of GAPDH transcript and protein increase in the cytosol and the nucleus in an isoform specific fashion. Such changes strongly implicate the role of GAPDH in yeast apoptosis. This work provides evidence for the involvement of targeted protein oxidation in metal toxicity, shows the overlaps and differences in the mechanism of copper and cadmium toxicity, allows comprehension of how metabolic processes respond to metal stress and explores the potential of GAPDH as a sensor of oxidative stress and mediator for apoptosis.

Metal mines release treated effluents that contain a variety of metals, metalloids, and organics into the aquatic environment. A number of metal mine effluents (MMEs) have been found to contribute to adverse effects in fish and benthic invertebrates, such as decreased diversity and density, however the specific causal factors of toxic responses during chronic exposures to the MMEs are often unknown. Therefore, the overall objective of this dissertation was to explore causative and modifying factors of MME toxicity to a resident fish species, the fathead minnow (Pimephales promelas), during chronic, multi-trophic exposures. The representative MME used in this study was the process water effluent (PWE) of a Canadian metal mine, which is released into Junction Creek in Sudbury, Ontario, Canada. Chronic exposure to the MME has been a source of decreased reproductive output in fathead minnows in several previous studies, however, these same studies were not able to determine the potential causal factors of the reproductive impairment. In order to address the overall objective, several laboratory mesocosm studies were conducted, which consisted of three separate components. The first component included exploring several metals (Cu, Ni, and Se; alone and in mixture) that are consistently present in the MME and are known to cause toxicity at fairly low concentrations as potential causes for decreased egg production in fathead minnows. The second component included evaluating the role of decreased food availability (a possible indirect effect of MME in the receiving environment) as a potential cause of decreased egg production in fathead minnows. The third and final component included examining the role of water chemistry [(increased alkalinity and dissolved organic carbon (DOC)] as potential modifying factors of chronic MME toxicity to fathead minnows. In general, my results suggest that the metals present in the MME likely do not contribute directly to decreased reproductive performance in fathead minnows during chronic exposures, under the conditions examined. Instead, the MME appears to decrease food availability, therefore indirectly influence fathead minnow egg production. Furthermore, water chemistry modifications tested in this thesis were not able to entirely mitigate the reproductive effects in fish induced by the MME, although they did improve egg production relative to unmodified MME. Metal concentrations in fish tissues were not influenced by increases to alkalinity or DOC level in the exposure water, suggesting that bioavailability of metals during chronic exposure to metal-mixtures cannot be fully explained based on our understanding of metal complexation with abiotic ligands (inorganic and organic) during single metal or acute exposures. From a regulatory perspective, water chemistry modifications may somewhat improve fathead minnow reproductive performance during chronic exposure to the MME, however the MME would still not be entirely free of effects relative to the uncontaminated water. Future studies should focus on understanding the factors responsible for decreased food availability in MME-impacted aquatic ecosystems, and further explore potential approaches for ameliorating effluent quality.

abstract: Due to analytical limitations, thermodynamic modeling is a lucrative alternative for obtaining metal speciation in chemically complex systems like life. However, such modeling is limited by the lack of equilibrium constant data for metal-complexation reactions, particularly for metal-organic species. These problems were ameliorated estimating these properties from 0-125°C for ~18,000 metal complexes of small molecules, proteins and peptides. The estimates of metal-ligand equilibrium constants at 25°C and 1 bar were made using multiple linear free energy relationships in accordance with the metal-coordinating properties of ligands such as denticity, identity of electron donor group, inductive effects and steric hindrance. Analogous relationships were made to estimated metal-ligand complexation entropy that facilitated calculation of equilibrium constants up to 125°C using the van’t Hoff equation. These estimates were made for over 250 ligands that include carboxylic acids, phenols, inorganic acids, amino acids, peptides and proteins. The stability constants mentioned above were used to obtain metal speciation in several microbial growth media including past bioavailability studies and compositions listed on the DSMZ website. Speciation calculations were also carried out for several metals in blood plasma and cerebrospinal fluid that include metals present at over micromolar abundance (sodium, potassium, calcium, magnesium, iron, copper and zinc) and metals of therapeutic or toxic potential (like gallium, rhodium and bismuth). Metal speciation was found to be considerably dependent on pH and chelator concentration that can help in the selection of appropriate ligands for gallium & rhodium based anticancer drugs and zinc-based antidiabetics. It was found that methanobactin can considerably alter copper speciation and is therefore a suitable agent for the treatment of Wilson Disease. Additionally, bismuth neurotoxicity was attributed to the low transferrin concentration in cerebrospinal fluid and the predominance of aqueous bismuth trihydroxide. These results demonstrate that metal speciation calculations using thermodynamic modeling can be extremely useful for understanding metal bioavailability in microbes and human bodily fluids. / Dissertation/Thesis / Doctoral Dissertation Biochemistry 2019

Coins occasionally cause health problems. These have a wide range of presentations and can affect multiple organ systems. This article presents a review of the medical literature addressing health problems caused by coins. These problems can be categorized as follows: (1) respiratory manifestations of ingested coins, (2) gastrointestinal manifestations of swallowed coins, (3) systemic effects of swallowed coins, (4) clinical management of swallowed coins, (5) allergic manifestations of coin exposure, and (6) miscellaneous health issues related to swallowed coins.

No description available.

No description available.

Thesis (PhD)--Stellenbosch University, 2011. / ENGLISH ABSTRACT: The terrestrial Oligochaete species Eisenia andrei and Enchytraeus doerjesi were exposed to different concentration series of Cd and Zn, both separately and in mixtures for 28 days in artificial OECD soil at 15, 20 and 25°C. At the end of the four week exposure period, survival and reproduction were assessed in E. doerjesi and survival, reproduction, biomass change, metal uptake and biomarker responses (MTT and comet assays) in E. andrei. Survival results for both E. andrei and E. doerjesi indicated that the lethality of Cd increased at higher temperatures, whereas the opposite was observed for Zn.Cadmium LC50 values were the highest at 15°C and the lowest at 25°C. In the Zn exposures LC50 increased with increasing temperature. Mixture results in both test organisms indicated that mixtures were less lethal than the metals separately. Effects of mixtures on survival, nonetheless, increased with increasing temperature. In the Cd experiment, reproduction in E. andrei was only recorded in the control treatments at the three temperatures investigated. However, the deleterious effect of Zn on the reproduction of both E. andrei and E. doerjesi decreased with increasing temperature and Zn EC50 for reproduction increased with increasing temperature. Results for exposures to mixtures indicated in both test organisms that the interaction between Cd and Zn were antagonistic. In both E. andrei and E. doerjesi, the effect of mixture exposures on reproduction decreased with increasing temperatures. The highest mixture EC50 values for reproduction were found at higher temperature. In E. doerjesi (using reproduction results in MixToxModules) Cd and Zn interactions were dose level dependent at the three temperatures investigated. Antagonism was the predominant interaction at lower mixture concentrations whereas synergism occurred at mixture concentrations equal to or higher than the mixtures’ EC50 values. Biomass loss increased with increasing temperature in the Cd exposures (p 9 0.05) but not in the Zn exposures in E. andrei. In this species mixture results indicated antagonistic interactions between Cd and Zn at all temperatures investigated. The deleterious effect of mixtures on the biomass of E. andrei increased with increasing temperature. When Cd and Zn interactions were further investigated in E. andrei (using biomass results in MixToxModules) it was found that they were dose level dependent at the three temperatures investigated. Antagonism was the predominant interaction at lower mixture concentrations whereas synergism occurred at mixture concentrations higher than the mixtures EC50 values. The assessment of metal uptake in E. andrei revealed a temperature dependent Cd uptake with higher Cd body burdens occurring at higher exposure concentrations and temperatures (p ≤ 0.05). In the case of Zn, although uptake was lower at higher temperature, there was no statistical difference in uptake between exposure concentrations and between temperatures. Mixture results however indicated that in mixture exposures less Cd was accumulated by E. andrei than in single Cd exposures (p ≤ 0.05). Inversely, in mixture exposures more Zn was accumulated by E. andrei than in single Zn exposures (p ≤ 0.05). Biomarker studies revealed that Cd and Zn were both cytotoxic and genotoxic whether in single or mixture exposures. Factorial ANOVA analyses of the effects of temperature and metals on the reduction of MTT by E. andrei indicated that temperature rather than the metals was the most important factor controlling mitochondrial activity (p < 0.001). In both Cd and Zn exposures significant deleterious metal effects on mitochondrial processes were found to increase with temperature (p ≤ 0.01). Mixture exposures indicated decreasing cytotoxicity with increasing temperature (p ≤ 0.05) and possible antagonism between Cd and Zn at cellular level. Results of the comet assay showed that the genotoxic profile of Cd was the opposite of the genotoxic profile of Zn. Cd was less genotoxic at lower temperature and increasingly deleterious at higher temperature while Zn was more genotoxic at lower than higher temperature (p ≤ 0.05). The results of mixture exposures indicated decreasing mixture genotoxicity with increasing temperature and suggested that the interactions between Cd and Zn at molecular level were probably antagonistic. / AFRIKAANSE OPSOMMING: Eisenia andrei en Enchytraeus doerjesi is aan verskillende konsentrasiereekse van Cd en Zn, afsonderlik en in mengsels, vir 28 dae in OECD kunsmatige grond onderskeidelik by 15, 20 en 25°C blootgestel Die volgende eindpunte is aan die einde van die vier weke blootstellingsperiode gemeet: oorlewing en voortplanting (by E. doerjesi) en oorlewing, voortplanting, biomassaverandering, metaalopname, MTT en komeettoetse (by E. andrei). Oorlewingsresultate by beide E. andrei en E. doerjesi het getoon dat toenemende temperatuur die letale toksisiteit van Cd laat toeneem terwyl die teenoorgestelde waar was vir Zn. By die Cd blootstellings was die LK50 waardes die hoogste by 15°C en die laagste by 25°C. By die blootstellings aan Zn het die LK50 waardes toegeneem by hoër temperatuur. Resultate by die mengsels by beide toestspesies het aangetoon dat die mengsels minder letaal was as die afsonderlike metale. Effekte van mengsels op oorlewing het nietemin toegeneem met toenemende temperatuur. By die Cd blootstellings is voortplanting slegs by die kontroles en in die geval van E. andrei by die drie onderskeie temperature ondersoek. Die nadelige uitwerking van Zn op voortplanting by beide E. andrei en E. doerjesi het afgeneem met stygende temperatuur en die Zn LK50 vir voortplanting het toegeneem met toenemende temperatuur. Resultate van die blootstellings aan mengsels het getoon dat die wisselwerking tussen Cd en Zn by beide spesies antagonisties was. By beide spesies het die invloed van die mengsels op voortplanting afgeneem met stygende temperatuur. Die hoogste mengsel LK50 waardes vir voortplanting is by hoër temperature gevind. By E. doerjesi was Cd en Zn wisselwerkings by blootstelling aan mengsels (voortplantingsresultate ondersoek deur van MixToxModules gebruik te maak) dosisvlak verwant by die drie temperature wat ondersoek is. Antagonisme was die oorwegende wisselwerking by laer mengsel konsentrasies terwyl sinergisme voorgekom het by mengsel konsentrasies gelyk aan of hoër as die LK50 waardes van die mengsels. In die geval van die Cd blootstellings by E. andrei het biomassaverlies toegeneem met toenemende temperatuur (p ≤ 0.05) maar nie by die Zn blootstellings nie. Resultate van blootstellings aan mengsels het getoon dat die uitwerking van mengsels op die biomassa van E. fetida toegeneem het met toenemende temperatuur. By die verdere ondersoek van Cd en Zn wisselwerkings, waar gekyk is na dosis verhouding of dosisvlak antagonisme (deur van biomassa resultate in MixToxModules gebruik te maak), is gevind dat Cd en Zn wisselwerkings dosisvlak afhanklik was by die drie temperature wat ondersoek is. Antagonisme was die oorwegende wisselwerking by laer mengselkonsentrasies terwyl sinergisme voorgekom het by mengselkonsentrasies hoër as die mengsel EK50 konsentrasies. Die bepaling van metaalopname deur E. andrei het ’n temperatuurafhanklike opname van Cd getoon met hoër Cd liggaamskonsentrasies by hoër blootstellingskonsentrasies en temperature (p ≤ 0.05). Alhoewel Zn opname laer was by hoër temperatuur was daar geen statisties betekenisvolle verskille in opname tussen blootstellingskonsentrasies of temperature nie. Die bepaling van metaalopname by wurms wat aan mengsels blootgestel is, het getoon dat minder Cd deur E. andrei opgeneem is as waneer die wurms aan Cd as enkelmetaal blootgestel is (p ≤ 0.05), Daarteenoor het die teenoorgestelde gebeur in die geval van Zn, Meer van die metaal is opgeneem wanneer E. andrei aan mengsels blootgestel is as aan die enkelmetaal. Biomerkerstudie het getoon dat Cd en Zn beide sito- en genotoksies kan wees ongeag of dit as enkelmetale of in mengsels toegedien is. Faktoriale ANOVA analises van die effekte van temperatuur en metale op die verlaging van MTT by E. andrei het getoon dat temperatuur ’n belangriker faktor was as metaalbesoedeling by die kontrole van mitochondriale aktiwiteit. (p ≤ 0.001). By beide Cd en Zn blootstellings was daar in elk geval statisties betekenisvolle metaaleffekte op mitochondriale prosesse met toename in temperatuur (P ≤ 0.01). By blootstellings aan mengsels is gevind dat sitotoksisiteit afgeneem het met toenemende temperatuur (p ≤ 0.05) asook ’n moontlike antagonisme tussen Cd en Zn op sellulêre vlak. Resultate van die komeettoets het getoon dat die genotoksiese profiel van Cd die teenoorgestelde was as die van Zn. Cd was minder genotoksies by laer temperature en meer en meer skadelik by hoër temperature terwyl Zn meer genotoksies was by laer as by hoër temperature (p ≤ 0.05). Die resultate van blootstlling aan mengsels het laer genotoksisiteit getoon met toename in temperatuur. Dit dui daarop dat wisselwerkings tussen Cd en Zn op molekulêre vlak moontlik antagonisties was.