Dissertations / Theses on the topic 'Arsenic cycle'

The presence of arsenic in drinking water has been a major concern for years, due to its concentration being above the maximum allowable limit of 10 μg/l. Ingestion of arsenic-contaminated water causes different types of cancer, cardiovascular diseases, skin lesion and more. Many techniques have been developed and used to reduce arsenic levels to the maximum allowable limit. The conventional methods to do so are adsorption, membrane filtration, coagulation-flocculation, oxidation, and ion exchange. The most common adsorption material is activated carbon produced from hard coal, but there is a shift towards using agro-waste materials in order to produce a more environmentally-friendly adsorbent with high rejection levels. Such materials include cocoa pod husk, ice cream beans, and red mombin seeds, where cocoa pod husk AC was able to remove 80% of arsenate, and red mombin seeds AC removed arsenate almost completely. Nanofiltration membranes were reportedly effective for arsenic removal, reaching a removal percentage of 90%. In this work, a life cycle assessment analysis using SimaPro was conducted for arsenic removal using red mombin seeds activated carbon and spiral wound nanofiltration membranes, as they are able to reach high removal efficiencies. The methods were then compared based on their impacts on the different environmental and damage categories to determine which is the better option. The results showed that nanofiltration had the lowest environmental impacts over the different impact categories by a huge difference
Juomaveden sisältämä arseeni on ollut merkittävä ongelma jo pitkään, sillä arseenipitoisuus ylittää usein sille asetun raja-arvon 10 μg/l. Arseenipitoisen juomaveden käyttö aiheuttaa muun muassa syöpä- ja verenkiertoelimistön sairauksia sekä iho-ongelmia. Juomaveden arseenipitoisuuden vähentämiseksi on kehitetty useita menetelmiä, joista tavallisimpia ovat adsorptio, kalvoerotus, koagulaatio ja flokkaus, hapetus ja ioninvaihto. Yleisin adsorptiomateriaali on aktiivihiili, joka on valmistettu kivihiilestä, mutta nykyisin maatalousjätteestä valmistetut adsorbentit ovat kiinnostuksen kohteena, sillä ne ovat ympäristöystävällisempiä ja niiden avulla voidaan saavuttaa korkea haitta-aineiden poistoprosentti. Tällaisia materiaaleja ovat muun muassa kaakaopavun kuoret ja punamombinin siemenet. Tutkimuksissa on saavutettu kaakaopavun kuorista valmistetun adsorbentin avulla 80 %:n poistuma arseenille ja punamombinin siemenet ovat poistaneet vedestä arseenin lähes kokonaan. Nanosuodatuksessa kalvot ovat tutkimusten mukaan poistaneet arseenista 90 %. Tässä tutkimuksessa suoritettiin SimaPro-ohjelmiston avulla elinkaariarviointi kahdelle vedenkäsittelymenetelmälle: adsorptiolle, jossa käytettiin punamombinin siemenistä valmistettua adsorbenttia, sekä nanosuodatukselle, jossa käytettiin spiraalikalvoja. Menetelmiä verrattiin niiden ympäristövaikutusten perusteella parhaan vaihtoehdon löytämiseksi. Tulosten perusteella nanosuodatuksen ympäristövaikutukset kaikissa vaikutusluokissa olivat merkittävästi alhaisemmat

Arsenic (As) is a highly toxic chemical that is widely distributed in groundwater around the world. As-bearing sulfide minerals (ASM) are known to contribute to high background concentrations of As in groundwater in regions where the geochemistry of the parent material is dominated by sulfide minerals. The fate of As in groundwater depends on the activity of microorganisms which can oxidize arsenite (Asᴵᴵᴵ), or reduce arsenate (Asᵛ). In oxidizing environments, Asᵛ is the predominant species, and the accumulation of As is limited by the sorption of As onto iron (Fe) oxides and hydroxides. Under reducing environments, Asᴵᴵᴵ is the predominant specie, and while the sorption strength of Asᴵᴵᴵ on the Fe-surface of Fe (oxy)hydroxides is weaker, the accumulation of As in water can be limited by the precipitation of As as part of an ASM. The main aim of this research is to study the impact of microbial activity on the mobilization and immobilization of As in the environment. The first objective of this research was to characterize the metabolic activity of three Asᴵᴵᴵ-oxidizing bacteria, Azoarcus sp. pb-1 strain EC1, Azoarcus sp. pb-1 strain EC3 and Diaphorobacter sp. pb-1 strain MC, isolated from a non-contaminated, pristine environment. These Asᴵᴵᴵ-oxidizing bacteria demonstrated a great metabolic flexibility to use oxygen and nitrate to oxidize Asᴵᴵᴵ as well as organic and inorganic substrates as alternative electron donors (e-donors) explains their presence in non-As-contaminated environments. The findings suggest that at least some Asᴵᴵᴵ-oxidizing bacteria are flexible with respect to electron-acceptors and e-donors and that they are potentially widespread in low As concentration environments. The second objective of this research was to investigate the stability of orpiment (As₂S₃) and arsenopyrite (FeAsS), at circumneutral pH and 30°C, under aerobic- and or anoxic conditions (nitrate amended as electron acceptor (e-acceptor)), in order to assess the feasibility of immobilizing As by formation of ASM as a long-term option for the bioremediation of As contamination. The percentage of As released from the minerals ranged from zero when FeAsS was biologically incubated to 87% for As₂S₃(s) under anoxic abiotic conditions. While the dissolution of ASM was greater in biological conditions, the presence of inoculum provided as sludge served as a sink for As, limiting the mobilization of As into aqueous phase. Thus, the mobilization of As from ASM can be controlled by altering the environmental conditions such as the redox conditions or by stimulating microbial activity. Further research investigated the formation of ASM catalyzed by biological reduction of Asᵛ and sulfate (SO₄²⁻). In particular, the third objective of this research was to study the effect of the pH on the removal of As due to the biological-mediated formation of ASM in an iron-poor system. A series of batch experiments were performed to study the reduction of SO₄²⁻ and Asᵛ by an anaerobic mixed culture in a range of pH conditions (6.1-7.2), using ethanol as the e-donor. A marked decrease of the total aqueous concentrations of As and S and the formation of a yellow precipitate was observed in the inoculated treatments amended with ethanol, but not in the non-inoculated controls, indicating that the As-removal was biologically mediated. The pH dramatically affected the extent and rate of As removal, as well as the stoichiometric composition of the precipitate. The precipitate was composed of a mixture of orpiment and realgar, and the proportion of orpiment in the sample increased with increasing pH. The results suggest that ASM formation is greatly enhanced at mildly acidic pH conditions. The fourth objective was to investigate the biomineralization of As through simultaneous Asᵛ and SO₄²⁻ reduction in a minimal iron environment for the As-contaminated groundwater bioremediation. A continuous bioreactor, inoculated with an anaerobic sludge was maintained at circumneutral pH (6.25-6.50) and fed with Asᵛ and SO₄²⁻, utilizing ethanol as an e-donor for over 250 d. A second bioreactor running under the same conditions but lacking SO₄²⁻ was operated as a control to study the fate of As removal. The reactor fed with both Asᵛ and SO₄²⁻ removed on the average 91.2% of the total soluble As, while less than 5% removal was observed in the control bioreactor without S. The biomineralization of As in the bioreactor was also evident from the formation of a yellow precipitate made of a mixture of As₂S₃ and AsS minerals. These results taken as a whole indicate that a bioremediation process relying on the addition of a simple, low-cost e-donor offers potential to promote the removal of As from groundwater by precipitation of ASM. The fifth objective was to evaluate the toxic impact that the exposure to soluble As or the formation of ASM could have on the anaerobic mixed culture used as inocula. The methanogenic community on the reactors was impacted by addition of As. The biogenic ASM inhibited the acetoclastic methanogens causing an accumulation of acetate. In the SO₄²⁻-free bioreactor, the methanogens were initially highly sensitive to Asᴵᴵᴵ (formed from Asᵛ reduction) but quickly adapted to its toxicity. Consequently, the formation of ASM would impact the methanogenic activity of an anaerobic biofilm, while the exposure to Asᴵᴵᴵ would not have a negative impact if the biofilm undergoes adaptation. The sixth and final objective was to study the stability of a biogenic ASM at two different pH values (6.5 and 7.5) and under different redox conditions. The long-term stability was evaluated in three different bioreactors that operated for 145 d: aerobic (R1), anoxic (nitrate as alternative e-acceptor (R2) and anaerobic (R3). The dissolution of ASM was greatly affected by the pH, and slightly by the presence and nature of the e-acceptor. The ASM was very stable at pH 6.5, however, the As mobilization rate was up to 7-fold higher at pH 7.5, likely due to the formation of thioarsenic species. The stability of ASM was also impacted by the e-acceptor present. The As mobilization rate was 77% higher under anaerobic conditions than under aerobic conditions, most likely due to the formation of secondary As-bearing minerals. Therefore, the stability of ASM depends on the conditions of the operation, and it can be controlled by altering the environmental conditions, such as the pH or the presence of the e-acceptor.

An indigenous mixed culture of bacteria collected from a Wastewater Treatment Plant (Brits, North West Province, South Africa), biocatalytically reduced Cr(VI) in the presence of As(III). Both the reduced chromium (Cr(III)) and the oxidised arsenic (As(V)) readily form amorphous hydroxides that can be easily separated or precipitated from the aqueous phase as part of the treatment process. Treatment of Cr(VI) and As(III) before disposal of wastewater is critical since both compounds are known to be carcinogenic and mutagenic at very low concentrations, and acutely toxic at high concentrations. Batch experiments were conducted to evaluate the rate of Cr(VI) reduction under anaerobic condition in the presence of its co-contaminant As(III) typically found in the groundwater and mining effluent. Results showed near complete Cr(VI) reduction under initial Cr(VI) concentrations up to 70 mg/L in a batch amended with 20 mg/L As(III). However, increasing Cr(VI) concentrations up to 100 mg/L resulted in the inhibition of Cr(VI) reduction activity. Further investigation was conducted in a batch reactor amended with 70 mg/L Cr(VI) concentration at different As(III) concentrations ranging from 5-70 mg/L to evaluate the effect of varying As(III) concentration on Cr(VI) reduction efficiency. Results showed that Cr(VI) reduction efficiency increased as As(III) concentrations increased from 5-40 mg/L. However, further increase in As(III) concentration up to 50 mg/L resulted in incomplete Cr(VI) reduction and decrease in Cr(VI) reduction efficiency. These results suggest that the rate of Cr(VI) reduction depends on the redox reaction of As(III) and As(V) with Cr(VI). Moreover, the inhibitory effect observed at high Cr(VI) and As(III) concentration may also be attributed to the dual toxicity effect of Cr(VI) and As(III) on microbial cell. From the above batch kinetic studies lethal concentration of Cr(VI) and As(III) for these strains was evaluated and established. Initial evaluation of the bacteria using 16S rRNA partial sequence method showed that cells in the mixed culture comprised predominantly of the Gram-positive species: Staphylococcus sp., Enterobacter sp., and Bacillus sp. The biokinetic parameters of these strains were estimated using a non-competitive inhibition model with a computer programme for simulation of the Aquatic System “AQUASIM 2.0”. Microbial reduction of Cr(VI) in the presence of As(III) was further investigated in continuous-flow bioreactors (biofilm reactor) under varying Cr(VI) loading rates. The reactor achieved Cr(VI) removal efficiency of more than 96 % in the first three phases of continuous operation at lower Cr(VI) concentration ranging from 20-50 mg/L. However, 20 % decrease in Cr(VI) removal efficiency was observed as Cr(VI) concentration increase up to 100 mg/L. The reactor was able to recover from Cr(VI) and As(III) overloading phase after establishing the resilient nature of the microorganism. Similarly to the batch reactor studies the overall performance of the reactor also demonstrated that the presence of As(III) greatly enhance Cr(VI) reduction in a bioreactor. This was evident by near complete removal of Cr(VI) concentration up to 50 mg/L. The basic mass balance expressions on Cr(VI) along with the non-competitive inhibition model were used to estimate the biokinetic parameters in the continuous flow bioreactor system. Cr(VI) reduction efficiency along the longitudinal column was also evaluated in this study. Results showed that Cr(VI) efficiency increased as Cr(VI) concentration travels along the longitudinal column. Other important factors such as oxygen and pH during biological Cr(VI) reduction in the presence of As(III) oxidation were also evaluated.
Dissertation (MEng)--University of Pretoria, 2014.
tm2015
Chemical Engineering
MEng
Unrestricted

Water is the essential part of every organism and it is also a vital constituent of healthy living and diet. Unfortunately water contamination over the past decade has increased dramatically leading to various diseases. As technology advances, we are detecting many pollutants at smaller levels of concentrations. Arsenic (As) is one of those major pollutants, and Arsenic poisoning is a condition caused due to excess levels of arsenic in the body. The main basis for Arsenic poisoning is from ground water which naturally contains high concentrations of arsenic. A case study from 2007 states that over 137 million people in 70 countries were affected by arsenic poisoning from drinking water [1]. This thesis work is motivated by this study and investigates the fabrication, characterization, and testing of Opuntia ficus-indica mucilage nanofiber membranes formed using a mucilage, polystyrene (PS) and iron oxide (Fe2O3) solution by an electrospinning process. Cactus mucilage is a jelly-like substance, which is extracted from the cactus pad, and is an inexpensive, biodegradable and biocompatible material. It is also an abundant material available in nature. Polystyrene is a synthetic aromatic polymer prepared from monomer styrene. Polystyrene is further dissolved using D-Limonene as a solvent. D-Limonene is a non-toxic solvent and is a citrus extract of orange peelings. In an effort to enhance adsorption capacity for the mucilage nanofiber membranes, iron oxide nanopowder is incorporated into the polymeric solution. A mucilage and polystyrene-iron oxide solution is mixed in different ratios and electrospun to obtain nanofibers. The fibers will be characterized by certain techniques such as Scanning electron microscopy (SEM), contact angle measurements, viscosity and Fourier transform infrared spectroscopy (FTIR). The fibers obtained from mucilage and PS-Fe2O3 will be further tested under Atomic fluorescence spectrometry (AFS) for testing the removal of arsenic from water. Also, a life cycle analysis (LCA) is conducted to evaluate the environmental impacts of the fabrication of the membranes by using SimaPro® software.

This work investigates the fabrication, characterization and testing of Opuntia ficus-indica mucilage nanofibers to be utilized in water filtration systems. These mucilage nanofibers are formed using different polymers through a process called electrospinning. The polymers used to promote the formation of nanofibers are poly vinyl alcohol (PVA) and polystyrene (PS). The mucilage is a jelly like substance extracted from the pads of the cactus plant. It is a mixture of proteins, complex polysaccharides and monosaccharaides. It is an inexpensive, non-toxic, biodegradable and biocompatible material which is present in abundance. The mucilage extracted from the pads is mixed with acetic acid to form the mucilage solution. The mucilage solution is then mixed by volume with co-spinning polymers, PVA and PS. PVA is a synthetic polymer that is water-soluble, and this work considers two types of PVA differentiated based upon molecular weight, such as low molecular weight PVA and high molecular weight PVA. Polystyrene is a synthetic polymer extracted from a monomer styrene, and it is inexpensive, biodegradable, and abundant. The polystyrene, in its solid form, is further decomposed using a solvent called D-Limonene. D-Limonene is a biodegradable, non-toxic solvent formed from the citrus extract of orange peelings. The PVA and PS solutions are mixed in several different volume ratios with the mucilage solutions. These solutions were electrospun and consistent nanofibers were obtained using the low molecular weight PVA solutions and the polystyrene solutions. The fibers and polymeric solutions were characterized by scanning electron microscopy (SEM), contact angle measurements, viscosity, and FTIR. Resulting mucilage nanofiber membranes were characterized by atomic fluorescence spectrometry (AFS) filtration testing. In addition, a life cycle analysis using the SimaPro software was performed to understand the environmental impact of solutions used to fabricate the mucilage nanofiber membranes. Characterization results confirm the formation of PVA:mucilage and PS:mucilage nanofibers. Filtration testing of the nanofiber membranes indicates better performance with membranes formed by PS: mucilage solutions as compared to PVA: Mucilage solutions. Overall, this work has shown that natural materials, such as cactus mucilage, can be synthesized with polymeric solutions to form environmentally friendly water filters.

THESIS ORGANISATION This thesis is organised into nine chapters that include seven international and national publications (six accepted and one submitted for publication). The initial overview chapter outlines the justification and direction for this thesis. With the exception of chapter 8 (accepted for publication on the 1st May 2005); all chapters are exact duplicates of published articles in international and national refereed journals (chapters 2 to 7). The initial chapters (2 and 3) presents research findings using a marine fish species, mullet (Mugil cephalus), to measure trace metal bioavailability in Lake Macquarie, NSW Australia. While subsequent chapters (4 to 8) are presenting research under taken to improve the understanding of arsenic cycling in marine and estuarine environments. The final chapter (chapter 9) is a synopsis of the major findings presented in this thesis. Due to the publication nature of this thesis, an unavoidable degree of replication exists within chapters (publications).

L'arsenic est un metalloïde toxique et cancérigène. Ubiquiste dans la pedosphere, il est très sensibleaux fluctuations des conditions redox du sol, ce qui influe significativement sa toxicité et mobilité. Nousétudions le cycle biogéochimique global de l'arsenic, en tenant compte de l'usage croissant des ressources, etpassons en revue l'importance respective de l'arsenic geogénique et anthropogénique dans l'environnement.La contamination à l'arsenic est souvent diffuse dans les bassins sédimentaires de l'Europe. Cependant, desconcentrations dans l'eau interstitielle du sol peuvent être élevées lors de périodes de saturation du solcausées par la monté des eaux souterraines ou les inondations, prévues d'augmenter dû aux changementsclimatiques. La spectrométrie de fluorescence X quantitative et sans standard a été utilisée pour analyserl'arsenic dans des sols relativement contaminés de la plaine alluviale de la Saône au moyen de protocoles depréparation d'échantillons conçus pour optimiser la précision d'analyse et l'exactitude in situ aux bassesconcentrations d'arsenic. L'arsenic dans ces sols est associe aux (hydr)oxydes du fer et de manganèse de lataille d'argile colloïdale. Ceux-ci subissent une dissolution réductrice par les microorganismes lors desinondations, libérant une importante concentration d'arsenic dans la phase aqueuse. Si, par la suite, l'arsenicdégagé n'est pas éliminé avec l'eau de crue évacuée, il est ré-immobilisé pendant l'oxydation du sol et lareprécipitation des oxydes métalliques. Grâce à une combinaison novatrice d'analyses chimiques par voiehumide, d'écologie microbienne, de spectroscopie ainsi que de modélisation thermodynamique et cinétique,nous démontrons que les cycles d'oxydo-réduction séquentiels entraînent une atténuation d'arsenic aqueuxdans des conditions réductrices dû à la coprécipitation croissante, et a une diminution de l'activitémicrobienne causée par l'appauvrissement en matière organique labile. Des processus d'atténuationsimilaires sont observés en l'absence d'activité microbienne pour Cr et As dans des argiles pyriteuses lorsquecelles-ci sont exposés aux oscillations redox provoquées par l'ajout de substances humiques réduites. Ainsi,nous montrons que les effets cumulatifs de cycles redox successifs sont extrêmement importants pour lamobilité de divers contaminants dans l'environnement.

Les déchets sulfurés issus de l’extraction des minerais métalliques génèrent des drainages miniers acides (DMA) contenant des éléments toxiques tels que l’arsenic. Les procédés de traitement passifs basés sur l’oxydation bactérienne du fer et de l’arsenic, en favorisant la précipitation de ces éléments sous une forme stable, pourraient représenter une solution efficace et économique pour traiter cette pollution. Dans ce contexte, l’objectif général de cette thèse était de mieux comprendre les facteurs environnementaux et opérationnels qui contrôlent l’efficacité d’élimination de l’arsenic. Une approche en pilote à flux continu a été mise en oeuvre afin de se rapprocher des conditions réelles d’un traitement. L’étude a été conduite d’abord à l’échelle d’un bioréacteur de paillasse en conditions contrôlées (température, lumière, débit, temps de séjour et hauteur d’eau), puis dans un dispositif de taille supérieure, fonctionnant de manière totalement passive et in situ. Ces dispositifs ont été alimentés avec de l’eau d’un DMA riche en arsenic, issue de l’ancien site minier de Carnoulès, dans le Gard. Les caractéristiques de l’eau et des bioprécipités au sein de ces pilotes, en particulier le rédox du fer et de l’arsenic, ont été suivis dans différentes conditions environnementales et d’opération par des méthodes de spéciation liquide et solide (HPLC-ICP-MS, EXAFS, XANES), des analyses minéralogiques (DRX) et des analyses microbiologiques (ARISA, séquençage haut débit du gène de l'ARNr 16S, quantification du gène aioA). Les résultats issus des expériences en laboratoire ont mis en évidence l’effet de différents paramètres opérationnels (hauteur d’eau, temps de rétention hydraulique, et présence/absence d’une pellicule flottante) sur les performances du traitement, ainsi que sur la microbiologie et la minéralogie des bioprécipités formés. Le dispositif de terrain a permis de tester les performances du procédé dans des conditions environnementales fluctuantes (variabilité de la physico-chimie de l’eau d’entrée et de la température) et d’acquérir des connaissances nouvelles sur l’évolution des bioprécipités au cours de six mois de traitement. Les connaissances acquises dans cette thèse pourront servir de base à la conception d’une étape d’élimination de l’arsenic dans les processus de traitement des DMA
Acid mine drainage (AMD) are produced by sulfuric tailings from mining of metal ores. They are characterized by high contents of toxic elements like arsenic. One efficient and economical solution for the treatment of As in these tailings could be the use of a passive method based on iron and arsenic bacterial oxidation, and the subsequent precipitation of these elements in a stable form. In this context, the objective of this PhD thesis was to better understand the environmental and operational factors controlling the efficiency of As removal processes. A continuous-flow pilot approach was implemented in order to better reproduce the real treatment conditions. This study was first performed in a bench-scale bioreactor with controlled conditions (temperature, light, flow, residence time and water height). Then, it was performed in a field-scale bioreactor installed in situ, reproducing a passive treatment in real conditions. These devices were fed with As-rich AMD waters from the ancient mine of Carnoulès (Gard, France). Water and bioprecipitate properties were monitored in both devices, specially the redox speciation of iron and arsenic. This monitoring was held for different environmental and operational conditions. Iron and arsenic speciation in liquid and solid phases was measured by different analytical techniques such as HPLC-ICP-MS, EXAFS and XANES. Mineral identification was made by XRD analysis, while microbiological characterization was made by ARISA, high-throughput sequencing of 16S rRNA gene, and aioA gene quantification. Results from the lab-scale experiments evidenced the effects of the different operational parameters (water height, hydraulic retention time and the presence/absence of a floating film) on the treatment performance, as well as on the microbiology and mineralogy of the produced bioprecipitates. The field device was used to test the treatment performance under fluctuating environmental conditions (variability of the physico-chemistry of the feed water and of the temperature) and to gain new knowledge about the evolution of the bioprecipitates during six months of treatment. All the knowledge acquired in this PhD thesis could serve as a basis for the design of an arsenic removal stage in DMA treatment processes

La destruction par brûlage de munitions chimiques de la Première Guerre Mondiale a provoqué une contamination importante de la partie supérieure du sol du site de la Place-à-Gaz par l’arsenic, le zinc, le cuivre et le plomb. Le traitement thermique a eu pour effet de minéraliser l’As des agents de guerre organoarséniés, et de former un assemblage minéral inattendu composé d’arséniates de Zn, Cu et Fe, et d’une phase amorphe riche en Fe, As, Zn, Cu et Pb. Ce matériel amorphe est la principale phase porteuse de l’As et des métaux dans la zone la plus polluée. Le site est sujet à des changements environnementaux pouvant affecter la stabilité des contaminants inorganiques. Afin d’évaluer l’impact d’épisodes de saturation en eau et de l’apport de matière organique sur les cycles biogéochimiques des métaux et de l’As, une étude en mésocosme a été menée. Les résultats montrent que la phase amorphe est instable en conditions saturées, et libère des contaminants dans l’eau interstitielle du sol. Comme sur le site, les contaminants les plus mobiles sont le Zn et l’As. L’addition de matière organique a induit une immobilisation de l’As, par piégeage de l’As V sur les oxyhydroxydes de fer, dans la partie saturée du sol. La caractérisation du compartiment microbien a été effectuée via des dénombrements, une analyse de la diversité bactérienne et des tests d’activités d’oxydation de l’As III et de respiration et. Les résultats montrent que les microorganismes ont contribué activement au métabolisme du C et de l’As. L’apport de matière organique a promu la croissance des microorganismes As III-oxydants et As Vréducteurs et modifié la structure des communautés bactériennes. Cependant, un effet négatif de la matière organique sur la vitesse d’oxydation de l’As III a été observé, entrainant une augmentation des concentrations d’As III en solution. Cette étude en mésocosme a montré que le dépôt naturel de litière organique a des conséquences antagonistes sur le transfert des contaminants inorganiques. Ces résultats fournissent de plus amples informations sur l’impact environnemental de la Grande Guerre et, de façon plus générale, sur les processus biogéochimiques contrôlant le comportement des métaux/métalloïdes sur les sites pollués
The thermal destruction of chemical munitions from World War I, on the site of “Place-à-Gaz”, induced intense local top soil contamination by arsenic and heavy metals. The heat treatment mineralized As from organoarsenic warfare agents, resulting in a singular mineral assemblage, composed of Zn, Cu and Fe arsenates and of an amorphous phase rich in Fe, As, Zn, Cu and Pb. The amorphous material was the principal carrier of As and metals in the central part of the site. The site undergoes environmental changes which may alter the stability of inorganic contaminants. To assess the impact of water saturation episodes and input of bioavailable organic matter on the biogeochemical cycles of metal(loid)s, a mesocosm study was conducted. Results showed that amorphous phase was instable in saturated conditions, and released contaminants in soil water. As previously observed on site, the most mobile contaminants were Zn and As. The addition of organic matter induced the immobilization of As by trapping of As V onto hydrous ferric oxides in the saturated soil. Microbial characterizations including counting, bacterial community structure, respiration, and determination of As IIIoxidizing activities were performed. Results showed that microorganisms actively contribute to the metabolisms of C and As.The addition of organic matter induced the increase of As III-oxidizing and As V-reducing microorganisms concentrations and modified the bacterial diversity. However, a negative effect of organic matter on the activity of As III oxidation was observed resulting in higher As III concentration in soil water. This study showed that the natural deposition of forest organic litter on the site, induced antagonist effects on the transfer of inorganic pollutants did not immobilize all the Zn and As and even contributed to As III transport to the surrounding environment. These results provide more information about the environmental impact of the Great War and more generally about the processes driving the behavior of metals/metalloids on polluted sites

On retrouve des contaminations d’aquifèr à l’arsenic dans touts les deltaï de l'Asie du Sud-Est, y compris dans le delta du Mékong, ce qui affecte la santé de millions de personnes. L’arsenic est très sensible aux fluctuations des conditions redox qui sont générés par les cycles alternés humides/secs pendant la saison de mousson. Une étude sur les caractéristiques géophysiques et chimiques du sol et des eaux souterraines dans le district de An Phu, dans le haut du delta du Mékong au Vietnam, suggère une forté contamination à l’As dans cette région. Les données chimiques et géophysiques indiquent une forte corrélation entre concentrations dans les eaux souterraines anoxiques et conductivité des sols. La liberation de l’arsenic est associée à la dissolution réductrice induih par des microorganisms des colloïdes et (oxyhydr)oxydes de fer dans des conditions d'oxydo-réduction oscillantes. La présence de bactéries sulforéductrices a le potentiel de stabiliser l’arsenic dans la phase solide et de l’atténuer dans la phase aqueuse par adsorption / désorption de l’arsenic sur les (oxyhydr)oxydes, et / ou sulfures de fer via la formation de complexes thiols. En raison de la teneur en pyrite élevée dans les sédiments, l'oxydation de la pyrite peut abaisser le pH et conduire à l'inhibition de la réduction microbienne du sulfate et aime empêcher la séquestration de l’arsenic dissous. Bien que le cycle biogéochimique de l’arsenic dans un système dynamique d’oxydoréduction soit une problématique complexe, il a été possible de renforcer notre compréhension de ce système
Aquifer arsenic (As) contamination is occuring throughout deltaic areas of Southeast Asia, including the Mekong Delta, and affects the health of millions of people. As is highly sensitive to fluctuations of redox conditions which are generated by the alternating wet-dry cycles during the monsoonal seasons. A survey of geophysical and chemical characteristics of soil and groundwater in the An Phu district, located in the vicinity of the Mekong Delta in Vietnam, shows the occurrence high As aqueous concentration in this region. Chemical and geophysical data indicate a strong positive correlation between As concentrations in the anoxic groundwater and conductivity of soils. In addition, mechanisms of As release are shown to be associated with colloidal and iron (oxyhydr)oxides which undergo microbial mediated reductive dissolution under redox oscilatting conditions. The presence of sulfate microbial reduction potentially stabilizes As in the solid phase and diminish As in the aqueous phase through the adsorption/desorption of As onto iron (oxyhydr)oxides and/ or sulfides with formation of thiols complexes in solid phase. Because of the high pyrite content in sediment, pyrite oxidation may drop in pH values, leads to inhibition of sulfate reducing bacteria and reduces sequestration of dissolved As. Although the biogeochemical cycling of redox sensitive species such as As in dynamic systems is challenging, it has been possible to strengthen our collective understanding of such system

碩士
國立高雄第一科技大學
環境與安全衛生工程所
94
ABSTRACT Gallium Arsenide (Ga/As) is one of the semiconductors called “compound semiconductor”. Arsine gas was used in the Ga/As epitaxy process. The arsenic exposure in the environment has been known to strongly relate to the health hazards. Previous studies on the work exposure of implanters in the semiconductor plants showed very low or no detection of arsenic in the air sampling. To further understand the work exposure of arsenic in the compound semiconductor plants, air sampling and analysis during tool maintenance were performed. Furthermore to understand the distribution of arsenic after the feed into the tool, wastewater sampling and analysis were performed to assess the life cycle of the arsenic in the whole process. Thus, this study comprised of two parts. The first part is the sampling and analysis of work exposure of arsenic. The second part is the assessment of life cycle of arsenic in the epitaxy process. The results show that all work exposure sampling and analysis were lower than the detection limits of 0.00236mg/m3, fulfill the requirement of current code requirement of 0.01 mg/m3. The maintenance staff can be protected properly from arsenic exposure if self-breathing apparatus were used at all time. However as most tools were arranged close to each other, other staff should be warned about the potential exposure. The life cycle results show that 7.14% of arsenic feed was deposit on the wafer or in the reaction chamber. 60.92% was collected in the process gas trap. The residual 31.73% entered the local scrubbers. Only 0.21% entered the central scrubber. The results were in consistent with the process gas trap where most exhaust materials should be trapped. Most wastewater containing arsenic should be converted into arsenic sludge. However, it should be noted that abnormal in the wastewater system may resulted in high concentration in the effluent.

Thesis (M.Sc.(Biochemistry)) -- University of Limpopo, 2019.
Retinoblastoma binding protein 6 (RBBP6) is the protein encoded by the Retinoblastoma Binding Protein 6 (RBBP6) gene that is located in chromosome 16p12.2. There is a growing list of newly discovered RBBP6 hypothetical splice variants but there are only three RBBP6 splice variants that are well documented. RBBP6 has been previously implicated in the regulation of cell cycle and apoptosis but little is known about the expression and regulation of the human RBBP6 splice variants during cell cycle progression and breast cancer development. This study was aimed at determining the expression pattern of RBBP6 alternatively spliced variants during arsenic trioxide-induced cell cycle arrest and apoptosis in breast cancer MCF-7 cells. It was also aimed at determining RBBP6 specific microRNAs and how they are regulated in MCF-7 breast cancer cells. MCF-7 cells were maintained and subjected to arsenic trioxide-induced cell cycle arrest and apoptosis. The MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) and the Muse™ Count & Viability assays were used to evaluate the effect of arsenic trioxide on the viability of MCF-7 cells. Cell cycle arrest using 11 μM arsenic trioxide and apoptosis using 32 μM arsenic trioxide were analysed using the MUSE® Cell Analyzer, light and fluorescence microscopy. Arsenic triode-induced apoptosis was analysed using the Muse™ Annexin V & Dead Cell Kit, MultiCaspase and MitoPotential assays using the Muse™ MultiCaspase Kit and Muse™ MitoPotential Kit. Arsenic trioxide-induced cell cycle arrest was analysed using the Muse™ Cell Cycle Kit. Semi-quantitative analysis of RBBP6 variants was carried out using the conventional Polymerase Chain Reaction (PCR), while the quantitative analysis was done using the Real-Time Quantitative PCR. The localization of RBBP6 isoforms was done using Immunocytochemistry (ICC). Web based Bioinformatics tools were used to identify RBBP6-specific microRNAs. The MTT results showed that arsenic trioxide decreased the viability of the MCF-7 cells in a dose-dependent manner. The Muse™ Cell Cycle analysis showed that 11 μM of arsenic trioxide induced G2/M cell cycle arrest in MCF-7 cells, while the Muse™ Annexin V & Dead Cell assay showed that 32 μM of arsenic trioxide induced the extrinsic apoptotic pathway in MCF-7 breast cancer cells. Using the conventional PCR, the MCF-7 cells were found to express the RBBP6 variant 1 transcript but lacks the expression of variant 2 and 3 transcripts, contrary to the kidney embryonic Hek 293 cells that exhibited the expression of RBBP6 variant 1, 2 and 3. Additionally, arsenic trioxide downregulated RBBP6 variant 1 in breast cancer cells during cell cycle arrest and apoptosis. The Real-Time PCR confirmed that MCF-7 cells lowly express RBBP6 variant 3. On the other hand, the ICC analysis showed that RBBP6 isoform 1 is localized and highly expressed in MCF-7 breast cancer cells. The Web based Bioinformatics tools showed that RBBP6 variant 1 specific microRNAs are down regulated in MCF-7 breast cancer cells. These results together showed that As2O3 is effective against MCF-7 cells and also regulated the expression of RBBP6 variants, especially, variant 1. This study showed that there are RBBP6 variants that are involved in breast cancer progression and there are those that may be involved in breast cancer suppression. Targeting these RBBP6 variants for therapeutic development is a promising strategy. In conjunction with RBBP6 expression, arsenic trioxide should be further explored as a breast cancer drug.

Lam Kin Bong Hubert.
Thesis (M.Phil.)--Chinese University of Hong Kong, 2004.
Includes bibliographical references (leaves 139-161).
Abstracts in English and Chinese.
Abstract (in English) --- p.i
(in chinese) --- p.iv
Acknowledgements --- p.vi
Publications --- p.ix
Table of Contents --- p.x
List of Tables --- p.xiii
List of Figures --- p.xiv
List of Abbreviations --- p.xvi
Chapter CHAPTER1： --- General Introduction --- p.1
Chapter Section 1.1 --- Historical Background and Application of Arsenic Trioxide as an Anti-cancer Agent --- p.1
Chapter Section 1.2 --- Arsenic Trioxide Induces Apoptosis in Cancer Cells --- p.3
Chapter 1.2.1 --- The Intrinsic and Extrinsic Pathways of Apoptosis Initiation --- p.4
Chapter 1.2.2 --- The Convergence of Pathways --- p.8
Chapter 1.2.3 --- Induction of Apoptosis by Arsenic Trioxide --- p.9
Chapter 1.2.3.1 --- Controversies in the Involvement of the Extrinsic Pathway --- p.9
Chapter 1.2.3.2 --- "Arsenic Trioxide, Oxidative Stress and the Mitochondria" --- p.10
Chapter 1.2.3.3 --- Caspase-3 Activation in Arsenic Trioxide-mediated Apoptosis --- p.12
Chapter Section 1.3 --- Arsenic Trioxide Perturbs the Cell Division Cycle --- p.13
Chapter 1.3.1 --- The Cell Cycle Oscillator --- p.14
Chapter 1.3.2 --- DNADamage and Cell Cycle Checkpoints --- p.15
Chapter 1.3.3 --- Induction of Cell Cycle Arrest by Arsenic Trioxide and its Association with Apoptosis --- p.17
Chapter Section 1.4 --- Acute Megakaryocytic Leukemia and Arsenic Trioxide --- p.20
Chapter CHAPTER 2： --- Objectives --- p.28
Chapter CHAPTER 3： --- Methodology --- p.30
Chapter Section 3.1 --- Materials --- p.30
Chapter Section 3.2 --- Methods --- p.39
Chapter 3.2.1 --- Culture of Megakaryocytic Cells and Their Treatment with Arsenic Trioxide --- p.39
Chapter 3.2.1.1 --- Maintenance of Cell Lines --- p.39
Chapter 3.2.1.2 --- Treatment with Arsenic Trioxide --- p.39
Chapter 3.2.2 --- "Effects of Arsenic Trioxide on Cell Proliferation, Apoptosis, Mitochondrial Integrity and Cell Division Cycle Profiles of Human Megakaryocytic Leukemia Cell Lines" --- p.40
Chapter 3.2.2.1 --- Trypan Blue Exclusion Assay --- p.40
Chapter 3.2.2.2 --- Quantitation of Externalized Phosphatidylserine --- p.41
Chapter 3.2.2.3 --- Quantitation of Active Caspase-3 Expression --- p.42
Chapter 3.2.2.4 --- Assessment of Mitochondrial Intensity --- p.42
Chapter 3.2.2.5 --- Analysis of Cell Division Cycle Profile --- p.43
Chapter 3.2.2.6 --- Analysis of Cell Cycle Kinetics by BrdU Labeling --- p.43
Chapter 3.2.2.7 --- Identification of Cell Cycle Specificity of Caspase-3 Expression --- p.45
Chapter 3.2.3 --- Effects of Arsenic Trioxide on the Expression of Apoptotic Signals in Human Megakaryocytic Leukemia Cell Lines --- p.45
Chapter 3.2.3.1 --- Effects of Arsenic Trioxide on mRNA Expression Levels of Apoptotic Regulators --- p.45
Chapter 3.2.3.2 --- Effects of Arsenic Trioxide on Protein Expression Levels of Apoptotic Regulators --- p.50
Chapter 3.2.3.2.1 --- Flow Cytometric Analysis --- p.50
Chapter 3.2.3.2.2 --- Western Blot Analysis --- p.51
Chapter 3.2.4 --- Effects of Arsenic Trioxide on Gene Expression Profiles of Human Megakaryocytic Leukemia Cell Lines By Microarray Analysis --- p.54
Chapter 3.2.5 --- Statistical Analysis --- p.57
Chapter CHAPTER 4： --- "Effects of Arsenic Trioxide on Cell Proliferation, Apoptosis, Mitochondrial Integrity and Cell Division Cycle Profiles of Human Megakaryocytic Leukemia Cell Lines" --- p.62
Chapter Section 4.1 --- Introduction --- p.62
Chapter Section 4.2 --- Results --- p.63
Chapter 4.2.1 --- Effects of Arsenic Trioxide on Proliferation Kinetics --- p.63
Chapter 4.2.2 --- Effects of Arsenic Trioxide on Cell Viability --- p.64
Chapter 4.2.3 --- Apoptosis-inducing Capability of Arsenic Trioxide --- p.65
Chapter 4.2.3.1 --- Quantitation of Externalized Phosphatidylserine --- p.65
Chapter 4.2.3.2 --- Quantitation of Active Caspase-3 Expression --- p.66
Chapter 4.2.4 --- Effects of Arsenic Trioxide on Mitochondrial Integrity --- p.67
Chapter 4.2.5 --- Effects of Arsenic Trioxide on Cell Division Cycle Profiles --- p.69
Chapter 4.2.6 --- Effects of Arsenic Trioxide on Cell Cycle Kinetics by Bromodeoxyuridine Labeling --- p.69
Chapter 4.2.7 --- Identification of Cell Cycle Specificity of Arsenic Trioxide-Induced Caspase-3 Activation --- p.71
Chapter Section 4.3 --- Discussion --- p.72
Chapter CHAPTER 5： --- Effects of Arsenic Trioxide on Apoptotic Signal Expression in Human Megakaryocytic Leukemia Cell Lines --- p.91
Chapter Section 5.1 --- Introduction --- p.91
Chapter Section 5.2 --- Results --- p.92
Chapter 5.2.1 --- Effects of Arsenic Trioxide on mRNA Expression Levels of Apoptotic Regulators --- p.92
Chapter 5.2.2 --- Effects of Arsenic Trioxide on Protein Expression Levels of Apoptotic Regulators --- p.94
Chapter 5.2.2.1 --- Flow Cytometric Analysis --- p.94
Chapter 5.2.2.2 --- Western Blot Analysis --- p.96
Chapter Section 5.3 --- Discussion --- p.96
Chapter CHAPTER 6： --- Effects of Arsenic Trioxide on Gene Expression Profiles of Human Megakaryocytic Leukemia Cell Lines by Microarray Analysis --- p.119
Chapter Section 6.1 --- Introduction --- p.119
Chapter Section 6.2 --- Results --- p.119
Chapter Section 6.3 --- Discussion --- p.122
Chapter CHAPTER 7： --- General Discussion and Conclusions --- p.135
BIblography --- p.139

Thesis (M.Sc. (Biochemistry)) -- University of Limpopo, 2019
Survivin is the smallest and a well-studied member of the inhibitors of apoptosis proteins (IAPs) family, which is involved in the regulation of cell division, inhibition of both caspasedependent and -independent apoptosis in cancer cells and promotion of angiogenesis. Survivin is detectable during embryonic and foetal development but is undetectable in normal adult tissues. It is, however, expressed in transformed cell lines as well as in most common types of human cancers. Regulation of survivin remains poorly understood, and the discovery of the regulatory biomolecules, microRNAs (MiRs) present an interesting opportunity to investigate the regulation of this protein and its variants in cancers, especially breast cancer. Additionally, the expression of the survivin splice variants during cell cycle progression and apoptosis is not fully understood. The aims of this study were to investigate the role of arsenic trioxide on the expression of survivin splice variants and their specific microRNAs during cell cycle progression and apoptosis in human breast cancer MCF-7 cells. The study also aimed at ascertaining the toxicity and efficacy of using coal fly ash-derived β-cyclodextrin carbon nanospheres to deliver arsenic trioxide into the MCF-7 cells. Carbon nanospheres (CNSs) were synthesised using a chemical vapour deposition method while arsenic trioxide was deposited using wet impregnation method to form the arsenic trioxide-β-cyclodextrin carbon nanospheres (ATO-β-cyclodextrin-CNSs). The formation of the CNSs and the loading of arsenic trioxide to CNSs were confirmed using scanning electron microscopy/energy dispersive X-ray detection (SEM-EDX). The in vitro cytotoxicity effect of the β-cyclodextrin carbon nanospheres (CNSs), arsenic trioxide and arsenic trioxide-β-cyclodextrin CNSs against KMST-6 and MCF-7 cells was analysed using the 3-(4, 5-dimethylthiazol-2-yl)-2, 5 diphenyltetrazolium bromide (MTT) Assay, Muse® Count and Viability Assay and light/fluorescence microscopy. Cellular apoptosis, cell cycle analysis, Multi-Caspase activation, mitochondrial membrane potential, MAPK activation and PI3K activation were analysed using the Muse® Cell Analyser. Polymerase Chain Reaction (PCR) and Immunohistochemistry were used to analyse survivin mRNA variants and protein expression, respectively. The survivin specific MiRs were predicted using both bioinformatics platforms and literature surveys. In order to understand the applicability of delivering arsenic trioxide for the treatment of breast cancer, skin fibroblast (KMST-6) and MCF-7 cells were exposed to β-cyclodextrin CNSs. The novel β-cyclodextrin CNSs did not show any cytotoxic effect on the KMST-6 cells but demonstrated such activity against the MCF-7 cells. More so, arsenic trioxide-βcyclodextrin CNSs were found to significantly reduce the viability of the MCF-7 cells and were shown to inhibit their cell growth through the induction of apoptosis. The MTT Assay results revealed arsenic trioxide inhibited the growth of the MCF-7 cells in a concentration-dependent manner. The Muse® Cell Analyser showed that arsenic trioxide induced G2/M cell cycle arrest and promoted cellular apoptosis without any damage to the mitochondrial membrane of MCF-7 cells. Furthermore, arsenic trioxide also deactivated two survival pathways, Mitogen-Activated Protein Kinase (MAPK) and Phosphoinositide 3-Kinase (PI3K) signalling pathways in MCF-7 cells. The deactivation of the two pathways was shown to be accompanied by the upregulation of survivin 3α during arsenic trioxide-induced G2/M cell cycle arrest and apoptosis. Survivin 2B was found to be upregulated only during arsenic trioxide-induced G2/M cell cycle arrest, but downregulated during arsenic trioxide-induced apoptosis. However, wild-type survivin was highly expressed in untreated MCF-7 cells, but the expression was upregulated during arsenic trioxide-induced G2/M cell cycle arrest and was downregulated during arsenic trioxide-induced apoptosis. Survivin variant ΔEx3 was undetected in both untreated and treated MCF-7 cells. Survivin 2α was upregulated during arsenic trioxideinduced apoptosis whereas, survivin 3B was only detected in the untreated MCF-7 cells. Additionally, survivin proteins were localised in both the nuclei and cytoplasm in MCF-7 cells and highly upregulated during arsenic trioxide-induced G2/M cell cycle arrest, which can be attributed to the upregulation of survivin-2B. Using TargetScan, MIRD and mirTarbase, a few MiRs were identified and confirmed to target wild-type survivin, survivin 2B and survivin ΔEx3. These include the MiR-542-3p and MiR-335-5p, which are both upregulated during apoptosis and MiR-218-5p, which is upregulated during cell arrest. MiR-218-5p targets survivin 2B, which was upregulated during G2M cell cycle arrest. The fly ash-derived CNSs can be used to deliver arsenic trioxide for therapeutic purposes, especially against breast cancer. Most importantly, these nanoparticles induced typical apoptotic characteristics in breast cancer MCF-7 cells. Arsenic trioxide can be used as therapeutic target for breast cancer treatment and nanotechnology can be used for its delivery. This study provided the first evidence that novel survivin 2B splice variant may be involved in the regulation of arsenic trioxide-induced G2/M cell cycle arrest only. This splice variant can therefore, be targeted for therapeutic purposes against Luminal A breast cancer cells

碩士
輔英科技大學
醫事技術系碩士班
95
To better understand the toxic effects and carcinogenic potency of nickel and arsenic, renal cells (LLC-PK1) were treated with various concentrations of nickel acetate [Ni(CH3COO)2 ] (0–480 μM) and sodium arsenite [NaAsO2] (0–8 μM) for 12, 24, 48, and 72 h. The cell death of LLC-PK1 induced by Ni(CH3COO)2 and NaAsO2 were concentration- and time-dependent. Increased generation of intracellular oxidant, lipid peroxidation, and apoptosis were observed in nickel or arsenic treated cells. This study showed that nickel and arsenic could cause the loss of mitochondria membrane potential (△Ψm) in LLC-PK1 cells that cause to mitochondria damage and cell apoptosis. Nickel and arsenic treatment were also altered cell cycle. After nickel and arsenic treatment, G2/M phase and Sub G1 were increased to comply with to rise in concentrations and time treated on LLC-PK1 cell. On the other hand, the cells modulated proteins that expressions of cytochrome c, p53 were increased, while Bcl-2, cdc-2, procaspase-9, and -3 were decreased in nickel-treated LLC-PK1 cells. After arsenic treatment, the expressions of cytochrome c, p53 were increased, while cdc-2, procaspase-9, and -3 were decreased but Bcl-2 not significant difference. These observations imply that oxidative stress, loss of mitochondria membrane potential (△Ψm), and alters on cell cycle underlie the mechanisms may play important role of nickel- and arsenic-induced renal toxicity.

The filtration and ultrafiltration experiment was applied on the stream water at the Mokrsko gold deposit and the results revealed that most of the elements were in the dissolved form and the 0,45 or 0,1 m filters could be used. During two 24-h field experiments, water samples were collected at 1-h intervals in order to prove the diel changes in the concentration and speciation of several trace elements. The determination of sorption processes at the surface of or within the veneer of biofilm has been determined by collecting natural and artificial priphyton. The results showed regular diel changes of As, Sb and Mo with highest concentrations occurring after the moon and the lowest concentrations in the early morning. The dissolved concentrations of other elements are conservative or their values were closed to their detection limits. The diel cycles are caused by changes in adsorption/desorption equilibria induced by diel cycles of temperature. The samples of biofilm revealed increased concentrations of the elements under the study and their diel variation were significant (approximatelly 35-96%); however, biofilm-controlled diel cycles of dissolved concentrations have not been proved.

As the demand for energy increases, competition for a sustainable alternative to non-renewable energy resources has resulted in the growth of the photovoltaic industry. Although most photovoltaic technologies are based on crystalline silicon, thin film technologies have been developed with the expectation of generating a comparably high-performing product with lower processing costs. These materials have demonstrated sufficiently high optoelectronic performance to enable commercialization but concerns such as material scarcity limit terawatt level power production.

碩士
台北醫學院
公共衛生學研究所
86
Inorganic arsenic has been considered to be a human carcinogen. However, ther eis little evidence for its carcinogenicity in animal models. In vitro studie sshowed that it is also a potent clastogen in a variety of mammalian cellsyste ms. In this study, the spontaneous sister chromatid exchanges (SCEs) inhuman p eripheral blood cells, and the flow cytometric DNA ploidy of humanurothelial c ells were used to identify the early biological effects that mayreveal genetic damage by arsenic.Two villages, Meicheng and Meifu of Lanyang Basin located o n the northeastcoast of Taiwan, were selected as study area. Most of the resi dents in thisstudy area still drink well water. Well water in the two study v illages werefound to have variant arsenic contents, ranging from non-detected to 3,464 ug/Lin Meicheng and non-detected to 2,177 ug/L in Meifu, respectively . Arseniccontents in well water were divided into four groups, including non- detected to10, 10.1-50, 50.1-299.9, and 300 ug/L or more. A total of 80 resid ents wererecruited as study subjects. However, only 48 residents agreed to pa rticipatethis study. The number of study subjects in each groups is 11, 11, 1 4, 12,respectively. After adjustment for age, sex and cigarette smoking, SCEs in the group with arsenic contents in well water more then 50 ug/L was signifi cantly higher thanthat in the group less than 10 ug/L. The SCEs of cumulative arsenic exposuremore than 2,000 ug/L-year were significantly higher than that of cumulativearsenic exposure less than 2,000 ug/L-year. SCEs was not positi vely correlated with internal exposure indices included arsenic concentration in urine, arseniccontents in hair and toenail. The replication index (RI) of human peripheralblood cells was positively associated with arsenic contents in well water. Atotal of 43 samples for urothelial cell cycle analysis were inc luded in this study. After adjustment for age and sex, arsenic content in blo od was significantly associated with the indices of cell cycle such as values of G0G1,S and G2M. However, various arsenic exposure indices did not show an y significantly association with these indices of cell cycle. Furthermore,ars enic content in blood has negative association with G0G, and positiveassociati on with S and G2M, showing that inorganic arsenic might interfere thecell cycl e.

abstract: Ion exchange sorbents embedded with metal oxide nanoparticles can have high affinity and high capacity to simultaneously remove multiple oxygenated anion contaminants from drinking water. This research pursued answering the question, “Can synthesis methods of nano-composite sorbents be improved to increase sustainability and feasibility to remove hexavalent chromium and arsenic simultaneously from groundwater compared to existing sorbents?” Preliminary nano-composite sorbents outperformed existing sorbents in equilibrium tests, but struggled in packed bed applications and at low influent concentrations. The synthesis process was then tailored for weak base anion exchange (WBAX) while comparing titanium dioxide against iron hydroxide nanoparticles (Ti-WBAX and Fe-WBAX, respectively). Increasing metal precursor concentration increased the metal content of the created sorbents, but pollutant removal performance and usable surface area declined due to pore blockage and nanoparticle agglomeration. An acid-post rinse was required for Fe-WBAX to restore chromium removal capacity. Anticipatory life cycle assessment identified critical design constraints to improve environmental and human health performance like minimizing oven heating time, improving pollutant removal capacity, and efficiently reusing metal precursor solution. The life cycle environmental impact of Ti-WBAX was lower than Fe-WBAX as well as a mixed bed of WBAX and granular ferric hydroxide for all studied categories. A separate life cycle assessment found the total number of cancer and non-cancer cases prevented by drinking safer water outweighed those created by manufacture and use of water treatment materials and energy. However, treatment relocated who bore the health risk, concentrated it in a sub-population, and changed the primary manifestation from cancer to non-cancer disease. This tradeoff was partially mitigated by avoiding use of pH control chemicals. When properly synthesized, Fe-WBAX and Ti-WBAX sorbents maintained chromium removal capacity while significantly increasing arsenic removal capacity compared to the parent resin. The hybrid sorbent performance was demonstrated in packed beds using a challenging water matrix and low pollutant influent conditions. Breakthrough curves hint that the hexavalent chromium is removed by anion exchange and the arsenic is removed by metal oxide sorption. Overall, the hybrid nano-sorbent synthesis methods increased sustainability, improved sorbent characteristics, and increased simultaneous removal of chromium and arsenic for drinking water.
Dissertation/Thesis
Doctoral Dissertation Civil and Environmental Engineering 2016

碩士
國立清華大學
生物科技研究所
92
Human apurinic/apyrimidinic endonuclease (APE), also termed redox factor-1 (Ref-1), is a multifunctional protein. However, the role of APE in regulating cell cycle progression and signal transduction pathway remains unrevealed. The APEas-CL3 cells that express an APE anti-sense gene enter M phase earlier and express more Cdc25C protein as comparison with the control Babe-CL3 cells. Under exposure G2 cells to sodium arsenite, the APEas-CL3 cells are more sensitive in the cytotoxicity and more easily to be recovered from the G2 delay as comparison with the Babe-CL3 cells. Arsenite induced G2 delay is correlated to Cdc25C degradation in both cell lines. However, after arsenite removal for 2 to 3 h, the Cdc25C protein levels in APEas-CL3 cells are higher than those in Babe-CL3 cells. Arsenite increases the phosphor-p53Ser15 and phospho-ERK protein levels in Babe-CL3, but not in APEas-CL3 cells. Furthermore, APE can interact with ERK in vitro and in vivo, and the interaction is enhanced by a reducing environment. Taken together, the present results suggest that APE participates in controlling G2/M transitional checkpoint during normal cell cycle progression and against arsenite-induced cell death by facilitating p53Ser15 and ERK phosphorylation mediated via upstream kinases.

The use of geosynthetic clay liners (GCLs) as (i) covers for arsenic-rich gold mine tailings and landfills, (ii) subsurface barrier for migration of hydrocarbons in the Arctic, and (iii) basal liner for sewage treatment lagoons were examined. After 4 years in field and laboratory experiments, it was found that best cover configuration above gold mine tailings might include a layer of GCL product with polymer-enhanced bentonite and a geofilm-coated carrier geotextile serving above the tailings under ≥ 0.7 m overburden. However, acceptable performance could be achieved with using a standard GCL with untreated bentonite provided that there is a minimum of 0.7 m of cover soil above the GCL. When GCL samples were exhumed from experimental landfill test cover with complete replacement of sodium in the bentonite with divalent cations in the adjacent soil, it was observed that the (i) hydraulic head across the GCLs, (ii) size of the needle-punched bundles, and (iii) structure of the bentonite can all significantly affect the value of the inferred in-situ hydraulic conductivity measured at the laboratory. The higher the hydraulic head and the larger the size of the needle-punched bundles, the higher the likelihood of internal erosion/structural change of bentonite at bundles that will cause a preferential flow for liquids to occur. A key practical implication was that GCLs can perform effectively as a single hydraulic barrier in covers provided that the water head above the GCL kept low. The hydraulic performance of a GCL in the Arctic was most affected by the location within the soil profile relative to the typical groundwater level with the highest increase in the hydraulic conductivity (by 1-4 orders of magnitude) for GCL below the water table. However, because the head required for jet fuel to pass through the GCL was higher than that present under field conditions, there was no evidence of jet fuel leakage through the barrier system. The leakage through GCLs below concrete lined sewage treatment lagoons was within acceptable limits, in large part, due to the low interface transmissivity between GCLs and the overlying poured concrete.
Thesis (Ph.D, Civil Engineering) -- Queen's University, 2014-02-28 08:53:29.171

O Apoio Logístico Integrado (ALI) é uma área já conhecida pela Marinha, que tem intenção de desenvolver um modelo de apoio de longo prazo a um projeto desenvolvido ou adquirido. O ALI, ao contrário daquilo que muitas vezes é a opinião comum, é mais do que simplesmente calcular os custos relativos ao ciclo de vida, apesar desta componente representar uma grande parte daquilo que efetivamente é o ALI. Esta ferramenta engloba também todo um estudo prévio que recai sobre a melhor forma de construção do projeto, englobando diversos estudos, como de fiabilidade, manutibilidade, testabilidade, entre outros. No entanto, quando se fala de um projeto adquirido, todos estes estudos assumem-se como realizados previamente, passando assim a tornar-se a preocupação central saber qual o custo que o projeto representa a longo prazo. Por forma a pôr em prática o estudo desta ferramenta, este trabalho realiza-se numa metodologia de estudo de caso, tendo-se utilizado um projeto decorrente na Arsenal do Alfeite, S.A. de desenvolvimento e construção de duas lanchas salva-vidas da classe “vigilante” como caso a ser estudado. Para apoiar na determinação do custo total das lanchas foi desenvolvido um modelo de Custo do Ciclo de Vida (CCV) das mesmas, com base nas necessidades assumidas a longo prazo pela Marinha e pela Arsenal do Alfeite, S.A. O produto final desta dissertação consiste na aplicação do cálculo do CCV às Lanchas “Vigilante”, exibindo todas as previsões de custos ao longo do período de vida útil das embarcações. É também realizado um estudo acerca das componentes que constituem o ALI, podendo esta informação ser utilizada quer pela Arsenal quer pela Marinha ou pelo Instituto de Socorro a Náufragos (ISN). O objetivo do cálculo do CCV destas lanchas permite ainda ter conhecimento das necessidades das mesmas com a antecedência necessária para que sejam tomadas decisões acertadas ao longo de todo o ciclo de vida.
The Integrated Logistic Support (ILS) is an area of knowledge already known by the Navy, that intents to develop a long-term model of support for a project developed or acquired. The ILS, contrary to what might be the general opinion, is more than just the computation of costs relative to the life cycle, although this represents a very important component of what effectively is the ILS. This tool also encompasses a previous study that lies on the best way to construct the project, including many diverse studies like reliability, maintainability, testability, among others. However, when we talk about a project acquired, all these studies are assumed to have been done previously, this way cost of the project in long term starts to be the most important concern. In order to put this tool to practice, this work is conducted in a case study methodology, in which it was chosen an ongoing project from the Arsenal do Alfeite, S.A. relative to the development and construction of two lifeboats of the “Vigilante” class to be used as the case being studied. To support the determination of the total cost of the lifeboats it was developed a cost model of the Life Cycle Cost (LCC), based on the long-term needs assumed by the Navy and by the Arsenal do Alfeite, S.A. The final product of this dissertation consists in the application of the LCC to the “Vigilante” lifeboats, displaying all the previsions made for the cost of all the lifeboat’s useful life. It is also presented a study of the components that make up the ILS, that can be used by the Arsenal, the Navy or the Instituto de Socorro a Náufragos (ISN). The goal of the LCC for these lifeboats is also to make it possible to know all the needs of the product with the necessary advance to make it easier to make successful decisions throughout the life cycle of the product.