Saccharomyces cerevisiae exhibits an apoptotic response upon exposure to toxic metals such as cadmium (Cd) and copper (Cu). Preliminary findings indicate that this response is dependent –to some extent- on the presence of a fermentable carbon source, glucose. To investigate this dependency we monitored the apoptotic response to both metals in the presence and absence of glucose and have shown that glucose is absolutely necessary in order to induce apoptosis in yeast at least during the exposure to metal. We have also looked at the biochemical changes that are taking place in yeast when treated with Cd using Fourier Transform Infra-Red (FTIR) Spectroscopy. Our results suggest that there are definitive changes in cellular activities that are discernable at 1660-1640cm-1 (amide I), 1540-1510cm-1 (amide II) and 1140-1080cm-1(DNA absorption bands).

Graduation date: 1993 / Figures in original are black and white photocopies. Best scan available.

Succinic acid, a low molecular weight dicarboxylic acid was used to leach out heavy metals from Willamette Valley soil (contaminated separately with lead, copper, and zinc) in form of water-soluble organo-metal complexes. The research tasks included developing synthetic contaminated soils representative of those found at Superfund sites and making heavy metal adsorption and desorption studies. Fixed amounts of single-metal contaminated soil were treated with succinic acid under varying conditions of pH and organic ligand concentration. Based on the total metal mobilized into the aqueous phase, the optimum values of pH and organic acid were established for each metal. Since the direct determination of all species solubilized by the organic acid solution was not possible, a computer speciation program called MICROQL was used to determine the concentration of metal species in solution containing several metals and potential ligands. The results indicate that succinic acid is capable of significantly altering the partitioning of metals between the soil and the aqueous phase. Higher concentrations of the organic acid resulted in higher removal of metal from the soil. In case of lead and copper, low pH (3.5) succinic acid flushing solution was found to be the most effective, while a pH range of 4.5-5.5 was deemed optimum for zinc. The results also established that the extent of removal of any metal depended not only upon the the stability constant of the organo-metal complex, but also on its mode of retention within the soil. / Graduation date: 1993

En aquest treball s'ha determinat l'efecte i la capacitat de captació dels metalls pesants (Pb i Cu) per part de diferents microorganismes fotòtrofs i heteròtrofs, mitjançant tècniques microscòpiques d'alta resolució per tal de seleccionar microorganismes com a indicadors de contaminació per metalls. Per a aquest objectiu, han estat seleccionats diferents microorganismes fotòtrofs aïllats dels tapets microbians del delta de l'Ebre (un ecosistema declarat Parc Natural al 1983) i cianobacteris de la col.lecció de cultius Pasteur (PCC). Aquests tapets on dominen els microorganismes fotosintètics com els cianobacteris i les algues (productors primaris en aquests ecosistemes) poden patir contaminació per compostos tòxics com ara el petroli o els metalls pesants. En aquest treball, els metalls assajats per a la selecció de bioindicadors, han estat el plom (Pb) i el coure (Cu) donat que tots dos s'han detectat en el riu Ebre, i també perquè el primer és molt tòxic i no presenta cap funció biològica i el segon és en canvi un element essencial a baixes dosis i tòxic a elevades dosis. Per determinar la sensibilitat a un metall (tolerància-resistència), s'ha utilitzat la microscopia làser confocal acoblada a un detector espectrofluoromètric (CLSM-λscan). Els resultats demostren que Chroococcus sp. PCC 9106 i la microalga DE2009 presenten una major tolerància a Pb (0.5 mM) que Oscillatoria sp. PCC 7515 i Spirulina sp. 6313 (0,1 mM). Per determinar la biocaptació externa i interna del metall, s'ha utilitzat la microscòpia electrònica de rastreig (SEM), la microscòpia electrònica de transmissió (TEM) i el microanàlisi d'energia dispersiva per raigs X (EDX) acoblada a aquests dos microscopis. Els resultats indiquen que, tots els microorganismes utilitzats (tant els fotòtrofs com els heteròtrofs) tenen la capacitat d'acumular Pb i Cu externament en el seu EPS. Finalment, l'anàlisi de les seccions ultrafines (TEM-EDX) mostra que tots els microorganismes fotòtrofs estudiats acumulen Pb en les inclusions de polifosfat (PP). Per contra, els bacteris heteròtrofs tot i presentar aquestes inclusions, no acumulen cap dels dos metalls, ni en el citoplasma ni en les inclusions intracel·lulars. Una vegada provada l'eficàcia d'aquestes tècniques microscòpiques tant en els microorganismes aïllats de l'ambient natural com en els de col.lecció, s'ha realitzat el mateix tipus d'assajos en microcosmos, amb l'objectiu d'obtenir bons bioindicadors de contaminació per metalls, tenint com a objectiu final la seva aplicació en l'ambient natural. En aquests experiments s'ha assajat únicament el Pb, i s'ha comprovat que igual que en els cultius, els microorganismes més abundants seleccionats en aquest sistema artificial, Lyngbya-like i Phormidium-like (cianobacteris) tenen la capacitat d'acumular aquest metall tant externa com internament i sempre en inclusions de PP. Considerant tots els resultats obtinguts es podria concloure que tots els cianobacteris i la microalga DE2009 analitzats podrien ser considerats bons indicadors de contaminació per metalls. No obstant això, Oscillatoria sp. i Microcoleus sp. han estat seleccionats per ser: els més abundants en l'ambient natural, de major grandària, tolerants a elevades concentracions de metalls i finalment per la seva capacitat d'acumular-los extra i intracel·lularment. / In this work, the effect and capacity to capture heavy metals (Pb and Cu) of different phototrophic and heterotrophic microorganisms have been studied through high-resolution microscopy techniques in order to select microorganisms as metal pollution indicators. For this purpose, different phototrophic microorganisms isolated from Ebro Delta microbial mats (an ecosystem declared as Natural Park in 1983) and cyanobacteria from the Pasteur culture collection (PCC) have been selected. These mats, dominated by photosynthetic microorganisms like cyanobacteria and algae (primary producers in these habitats) can suffer pollution by toxic compounds such as oil or heavy metals. In this study, metals tested to select the bioindicators were lead (Pb) and copper (Cu), as both have been detected in the Ebro River, and also because the former is very toxic, showing no biological function, while the latter, by contrast, is an essential element at low doses, while at high doses it is toxic. To determine the sensitivity to a metal (tolerance-resistance), confocal laser microscopy coupled to a spectrofluorometric detector (CLSM-λscan) has been used. The results show that Chroococcus sp. PCC 9106 and DE2009 microalgae show greater tolerance to lead Pb (0.5 mM) than Oscillatoria sp. PCC 7515 and Spirulina sp. 6313 (0.1 mM). To determine the external and intracellular metal biocapture, scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive Xray microanalysis (EDX) coupled with these microscopes have been used, respectively. The results indicated that, all the microorganisms tested (both phototrophic and heterotrophic) have capacity to accumulate Pb and Cu externally in the EPS. Finally, the analysis of ultrathin sections (TEM-EDX) shows that all the phototrophic microorganisms studied accumulate Pb in the polyphosphate inclusions (PP). By contrast, although the heterotrophic bacteria show these inclusions, they do not accumulate either of the two metals either in cytoplasm or in intracellular inclusions. Once the effectiveness of these microscopy techniques has been shown both in microorganisms isolated from the natural environment and in those from the culture collection, the same tests have been carried out in microcosms in order to obtain good bioindicators of metal pollution, with the ultimate aim of applying them in the natural environment. In these experiments it has been shown that, as in cultures, the most abundant microorganisms selected in this artificial ecosystem, Lyngbya-like and Phormidium-like (cyanobacteria), have the capacity to accumulate this metal both externally and internally, always in PP inclusions. Considering all the results obtained it can be concluded that all cyanobacteria and DE2009 microalga analysed could be considered good metal pollution indicators. However, Oscillatoria sp. and Microcoleus sp. have been selected as the best indicators of metal pollution in the natural environment because: they are the most abundant, largest in size, tolerant to high concentrations of metals and, finally, capable of accumulating metal extra- and intracellularly.

Lotsbroverket is the largest wastewater treatment plant on the Aland Islands and it isdesigned for handling wastewater from approximately 30 000 persons. In 2011,Lotsbroverket produced about 2800 m3 of dewatered sludge. The sewage sludge that isproduced is transported to a contractor where it is processed to eventually be used e.g.in the construction of green space. This study aims to investigate available applicationoptions in terms of the sewage sludge that is produced in Lotsbroverket. The main aimis to study the feasibility of using the produced sewage sludge as a fertilizer in theagriculture of the Aland Islands.The sludge already fulfills limit values for heavy metals in accordance with the Act"The Aland Government´s directive on the use of sewage sludge in agriculture." Inorder to clarify the sludge content of pharmaceutical and organic substances it isrequired that the substances are identified and a risk assessment is performed. In theliterature it is found that the risk of human exposure to these substances is low if thesludge is treated appropriately. Suggested appropriate treatment of the plant's sludge isthermophilic digestion whereby also pathogens are killed.The soil of the Aland Islands has a high content of phosphorus. Since 1995 there is anenvironmental program to which currently 95% of the island's farmers are connected.The program controls the use of fertilizers i.e. by setting maximum permitted levels ofphosphorus. Since sewage sludge contains relatively much phosphorus it may be alimitation of the use of sewage sludge on agricultural land of the Aland Island. That iswhy it would be suitable to use the sludge with a different fertilizer in order to obtainthe proper fertilizing properties.In Europe, the use of sewage sludge in agriculture is relatively widespread. Severalcountries have less strict laws regarding the sludge content than the Aland Islands.Because large amounts of fruits and vegetables annually are imported into the island,there is reason to believe that the population already consumes products grown onsludge treated soils. Several of the farmers on the Aland Islands are currently scepticalin terms of using sewage sludge in agriculture, mainly due to uncertainties in the sludgecontent. Regarding the certification of Lotsbroverket in accordance with the Swedishcertification system REVAQ no barriers have been found. To ensure that a certificationis possible, however, further investigations are required.

The research focuses on the fate of heavy metals and their emissions from pulp mill recovery boilers. Heavy metals are extremely toxic and cause adverse effects on human health. There is limited information about factors affecting heavy metal vaporization from recovery boilers, in which spent pulping liquors, (also called black liquor) is burnt. The heavy metals are present in trace quantities in black liquor. They are emitted in the air as submicron particles, and their amount of emission depends on the input of metals into the recovery boiler, volatilization of metals in the boiler and the efficiency of the electrostatic precipitator (ESP) to remove the metals. The heavy metals vaporization from different recovery boilers vary widely and the reason is not known. My thesis will focus on determining what conditions affect the volatility of the heavy metals, and whether differences in heavy metal vaporization are due to differences in boiler operating conditions or the composition of the liquor. I will examine black liquor pyrolysis, combustion and gasification in well-controlled laboratory conditions. I will analyze three different black liquors. The liquors will be spray-dried and burnt or gasified in a laminar entrained-flow reactor at high temperatures of 1000-1100C and residence times ranging from 0.5 to 1.5 s. Equilibrium calculations will be performed to determine the distribution of heavy metals and species under set conditions from previous devolatilization experiments. The equilibrium calculations will serve as a useful tool for prior estimation of the distribution of heavy metals. The impact of different liquors on volatilization of heavy metals in the experiments will be determined. The char residue and condensation aerosol (fume) particles from each experiment will be analyzed using ICP-AES. The amount of heavy metals volatilization during combustion and gasification will be determined based on the amount of the metals in the char residues and fume particles. Based on the results of the experimental study combined with data from the equilibrium analysis program the main cause of variability in heavy metal vaporization can be found. Also the boiler operating conditions can be studied to determine its affects on the volatility of the heavy metals.

Although soils developed from ultramafic parent materials have significance to agriculture, ecology and health, their bio-geochemistry is poorly understood. The mineralogical and bio-geochemistry of soils formed from the ultramafic parent materials of the Great Dyke, Zimbabwe and Gillespie County, Texas was investigated. The objectives were to determine the mineralogical and bio-geochemical properties of the soils in order to assess the potential impact and challenges to agriculture, and environmental quality. Soil samples were taken from the crest, shoulder, footslope and the toeslope. Chemical analyses were performed by nuclear and spectroscopic techniques. Mineral characterization was conducted by x-ray diffraction (XRD) and spectroscopic techniques. Microbial whole-community structure was determined by the fatty acid methyl esters (FAME) technique. The results indicate wide chemical and mineralogical compositions among the studied sites. The soils contain relatively high concentrations of heavy metals (some sites contain Cr(VI)), but low levels of K and Ca. The highest concentrations of trace metal were associated with chromite, Fe oxides and serpentinite. The concentrations of Mg were higher than those of Ca and varied between Zimbabwe and Texas soils largely due to the parent materials. Unique to these soils is the occurrence of talc, serpentine, chlorite, Fe-rich smectite, amphiboles, pyroxenes, Fe and Cr oxides in relatively large amounts. These soils also lack micas and have neglible amounts of kaolinite and feldspars. Palygorskite and serpentine occurred in specific soil horizons and at specific landscape positions. FAME profiles indicate that the soil microbial community structure is predominantly bacteria and fungi (including arbuscular mycorrhiza fungi) at each landscape position across the transect. Biomarkers for actinomycetes were undetectable. The proportions of Gram-positive bacteria were higher than those of the Gram-negative bacteria. Very low levels of nutrients (Ca and K), higher Mg/Ca molar ratios, and the relatively high concentrations of heavy metals in these soils impact agricultural productivity. High concentrations of heavy metals, the presence of the Cr(VI) as well as its great potential to form in these soils might impact microbial activity and environmental quality. The occurrence of fibrous minerals (e.g serpentine and amphiboles) in these soils will likely impact human health.

Electroplating industry is one important industries in Taiwan. Its wastewater has lead to pollution of the river, ocean, and underground water. Thus, the reduction of the concentration of heavy metals such as Cu, Zn, Ni, Cr, Pb etc. from wastewater is critical. Conventional strategies to remove the heavy metals involve adding abundant chemical agents which results in largy quantity of heavy metal sludge. Secondary pollution might occur as due to the heavy metal sludge contacted with acid. Aquatic plants have been shown to uptake the heavy metals from the surrounding environment. This unique character is different from the conventional approach and could be applied for removing the heavy metals in wastewater.This study used an aquatic plant, Najas graminea Del, to remove the heavy metals from the prepared metal solution and electroplating wastewater. Our data revealed that the relationship between the specific adsorption and residual concentration of the heavy metal was best described by the Langmiur adsorption isotherm curve. The value of maximal adsorption capacity (Ymax) in copper is 58.1 mg/g. Without buffering, the sequential order for the Ymax in the prepared metal solution is Cu > Pb > Cd> Ni > Zn. The value of Ymax was with significantly reduced under buffering circumstance as compared with that no buffer. In the electroplating wastewater containnig copper from company A, the value of Ymax was 20.7 mg/g, which was much smaller in prepared copper solution (Ymax =33.1 mg/g). Our further investigation showed that the background contaminatants especially iron in the electroplating wastewater have significant contribution to this discrepancy. In other set of experiments, we found that there is no significant difference between the electroplating wastewater and prepared solution for the adsorption of Ni. Our results provide useful information the understanding the process for the Najas graminea in adsorption the heavy metals from electroplating wastewater. Futhermore, the application of Najas graminea to remove the pollution from wastewater can protect the enviroment from pollution. This innovative concept has the potential in practical application and could be trasferred into a novel technology to substitute the conventionally physical or chemical treatment for the electroplating wastewater.

The research, first, is to investigate the characteristics and heavy metal content of sediments and bottom water in Kaohsiung harbor by sampling. Second, it is to analyze the correlation of the sediments data by statistics analysis method. According to the correlation ratio, we can try to explain the distribution of heavy metals in the sediments and the water. Finally, it is to analyze the sediments data in Kaohsiung harbor from the year of 2001 to 2004 by principle compounds analysis of multivariate statistical analysis; the purpose is to find out the main reason that causes the variation of the sediments in the harbor area. The result of the sediments analysis shows that, the pollutants in Jen-Gen River, Love River and Canon River deposit in the outlet area and lead to significant difference in spatial distribution of sediments characteristics and heavy metals content in Kaohsiung harbor. The enrichment factors of heavy metals in sediments indicate that, there are enrichments for Hg (EF = 7.9 - 115), Pb (EF = 2.1 ¡V 11.7), Cd (EF = 2.4 ¡V 29.8), and Zn (EF = 1.9 ¡V 19.8) in the harbor area. And there are differences of height in the spatial distribution. The Cr enrichment (EF = 1.1 - 10.9) in the harbor exists only in the nearby area of the river outlet, especially in station KH-10 (EF = 10.9) nearby Jen-Gen River area. There is Cu enrichment in the harbor area (EF = 1.2 - 9.0) except the First and Second Harbor Entrance stations. The correlate tests of the sediments characteristics to the heavy metal concentration show that, volatile solid materials, grease and heavy metals reach significant correlated level (P<0.05); but it is irrelevant between clay and heavy metals (P>0.05). Therefore, the main controlling factor that influences the distribution of heavy metals is not the sedimentary particulates distribution but the organic characteristics. Ni distribution of bottom water in Kaohsiung harbor area, it has higher concentration from station KH-01 to KH-10 (0.4 -1.0£gg/L); and, among them, it has the highest concentration and high variation at station KH-06 (1.0 ¡Ó 1.0£gg/L). The distribution of Cu average concentration is between 1.2 - 2.9£gg/L. There is no absolutely tendency, neither is significant difference. The result of the research on Ni, SiO2 and PO4 correlated analysis is different from the result of Yeats and Campbell (1983), Chung (1995) and Huang (2002). I conjecture that the course could be the different geographic environment (Yeats and Campbell in Atlantic, Chung and Huang in the southwestern waters of Taiwan, the research in Kaohsiung harbor area). The result of sediments principle compounds analysis shows that, the sediment constituents in 2001 and 2002 are high water content, organic and fine-grain organic polluted sediments. The polluted sediments are reduced in 2003 and 2004, and that accords with the time of the harbor area dredges procedures. Therefore, there is causation between them. From PC1 and PC2, we know that Love River (KH-04), Canon River (KH-06) and Jen-Gen River (KH-10) outlet are seriously polluted in the harbor area. The river water that contains the industrial wastewater and municipal wastewater in the upper stream is the most important reason that influences the harbor sediments. The result of the research shows that, the main controlling factor that influences the distribution of heavy metals is the harbor sediment organic characteristics and that could cause the metal ions and organic matter forming into stable organic metals compounds. Its impact to ocean ecosystem is enormous, especially to benthic system. Therefore, I suggest that we should do monitoring analysis on sediment toxicity or toxic organic compounds in order to realize their influences to the ocean ecosystem. And furthermore, we should realize the standing crop and the distribution of the toxic organic compounds so that we can avoid health harming from the accumulation of the ecological food chain returning to human body.

The electroplating wastewater is usually treated by chemical precipitation, and the generated sludge has loose structure to cause the difficulties in sedimentation and filtration. Moreover, the sludge is unstable and the contained heavy metals are easily leached. Solidification is one method to deal with this kind of sludge; however it cause another problem, land requirement. In this study, the contents of electroplating wastewater are divided into two parts organic matters and heavy metals; organic matters are treated by Fenton method and heavy metals are by Ferrite process. The purpose of this study is that through the serial Fenton-Ferrite Process treatment the effluent water and the sludge generated from the procedure could meet the standards in Taiwan. It was well-know that the primary operation factors of Ferrite Process are pH, reaction temperature, ferrous ion concentration, time and aeration. The results showed that the proper factors of FP were pH=10, temperature= 90¢J, Fe/M molar ratio= 7,reaction time=80 min and aeration rate=1.0 L air / min / L solution. However, in Fenton method, the parameters of pH, hydrogen peroxide, ferrous ion concentration, and reaction time were discussed. I had greatest efficiency under the data showed that Fenton method pH = 3, ferrous ion concentration=3000 mg/L, hydrogen peroxide = 13000 mg/L, and reaction time=2 hr. The wastewater measured COD =1162 mg/L, Cr=70 mg/L, Zn=400 mg/L. The treatment efficiency of the procedure combining Fenton method and Ferrite Process were that COD=88.5 mg/L, Cr=1.06 mg/L, and Zn=0.98 mg/Lin effluent water and the TCLP test results of sludge were Cr=3.37 mg/L, Zn=2.46 mg/L. All the data showed that the combination of the two process can significantly treat wastewater to meet the standards. Furthermore, the sludge can be recycled as magnetic materials or other purposes due to it¡¦s specific properties.