Natural organic matter and colloid-facilitated arsenic transport and transformation in porous soil media

Prediction of arsenic transport and transformation in soil environment requires understanding the transport mechanisms and proper estimation of arsenic partitioning tong all three phases in soil/aquifer systems: mobile colloids, mobile soil solution, and immobile soil solids. The primary purpose of this research is to study natural dissolved organic matter (DOM)/colloid-facilitated transport of arsenic and understand the role of soil derived carriers in the transport and transformation of both inorganic and organoarsenicals in soils. ^ DOM/colloid facilitated arsenic transport and transformation in porous soil media were investigated using a set of experimental approaches including batch experiment, equilibrium membrane dialysis experiment and column experiment. Soil batch experiment was applied to investigate arsenic adsorption on a variety of soils with different characteristics; Equilibrium membrane dialysis was employed to determine the 'free' and 'colloid-bound/complexed' arsenic in water extracts of chosen soils; Column experiments were also set up in the laboratory to simulate arsenic transport and transformation through golf course soils in the presence and absence of soil-derived dissolved substances. ^ The experimental results revealed that organic matter amendments effectively reduced soil arsenic adsorption. The majority of arsenic present in the soil extracts was associated with small substances of molecular weight (MW) between 500 and 3,500 Da, Only a small fraction of arsenic was associated with higher MW substances (MW > 3,500 Da), which was operationally defined as colloidal part in this study. The association of arsenic and DOM in the soil extracts strongly affected arsenic bioavailability, arsenic transport and transformation in soils. The results of column experiments revealed arsenic complicated behavior with various processes occurring in soils studied, including: soil arsenic' adsorption, facilitated arsenic transportation by dissolved substances presented in soil extracts and microorganisms involved arsenic species transformation. ^ Soil organic matter amendments effectively reduce soil arsenic adsorption capability either by scavenging 'soil arsenic adsorption sites or by interactions between arsenic species and dissolved organic chemicals in soil solution. Close attention must be paid for facilitated arsenic transport by dissolved substances presented in soil solution and microorganisms involved arsenic species transformation in arsenic-contaminated soils.^

A Market Study of Organic and Fair Trade Coffee in Bolivia

The purpose of this research is to study the commercialization of Fairtrade and Organic coffee in the Bolivia. Fairtrade and Organic coffee are alternative trade systems designed to promote the equitable and environmentally sustainable production of coffee. However, these alternative trading systems often fail to meet these goals. The producers and environment these systems are intended to protect remain marginalized. These failures are due to a number of local institutions. In order to better understand these institutions, this research conducted interviews of various stakeholders including producers, cooperative leaders, organic/Fair Trade certifiers, government agencies and private buyers. All these stakeholders influence the success of the alternative trade systems. By better understanding how these stakeholders impact the commercialization of coffee in Bolivia; new policies can be develop to improve the outcomes of alternative trade, to benefit both producers and the environment. This is especially critical in Bolivia because of the environmentally sensitive area in which coffee is grown, the potentially damaging impact of coca on the region and, the devastating economic impact to farmers.

The investigation of photocatalysts and iron based materials in the oxidation and adsorption of toxic organic and chromium materials

The presences of heavy metals, organic contaminants and natural toxins in natural water bodies pose a serious threat to the environment and the health of living organisms. Therefore, there is a critical need to identify sustainable and environmentally friendly water treatment processes. In this dissertation, I focus on the fundamental studies of advanced oxidation processes and magnetic nano-materials as promising new technologies for water treatments. Advanced oxidation processes employ reactive oxygen species (ROS) which can lead to the mineralization of a number of pollutants and toxins. The rates of formation, steady-state concentrations, and kinetic parameters of hydroxyl radical and singlet oxygen produced by various TiO2 photocatalysts under UV or visible irradiations were measured using selective chemical probes. Hydroxyl radical is the dominant ROS, and its generation is dependent on experimental conditions. The optimal condition for generation of hydroxyl radical by of TiO2 coated glass microspheres is studied by response surface methodology, and the optimal conditions are applied for the degradation of dimethyl phthalate. Singlet oxygen (1O2) also plays an important role for advanced processes, so the degradation of microcystin-LR by rose bengal, an 1O2 sensitizer was studied. The measured bimolecular reaction rate constant between MC-LR and 1O2 is ∼ 106 M-1 s-1 based on competition kinetics with furfuryl alcohol. The typical adsorbent needs separation after the treatment, while magnetic iron oxides can be easily removed by a magnetic field. Maghemite and humic acid coated magnetite (HA-Fe3O4) were synthesized, characterized and applied for chromium(VI) removal. The adsorption of chromium(VI) by maghemite and HA-Fe3O4 follow a pseudo-second-order kinetic process. The adsorption of chromium(VI) by maghemite is accurately modeled using adsorption isotherms, and solution pH and presence of humic acid influence adsorption. Humic acid coated magnetite can adsorb and reduce chromium(VI) to non-toxic chromium (III), and the reaction is not highly dependent on solution pH. The functional groups associated with humic acid act as ligands lead to the Cr(III) complex via a coupled reduction-complexation mechanism. Extended X-ray absorption fine structure spectroscopy demonstrates the Cr(III) in the Cr-loaded HA-Fe 3O4 materials has six neighboring oxygen atoms in an octahedral geometry with average bond lengths of 1.98 Å.

The Effect of Natural Products and Small Gtpases in Adipogenesis

Insulin signaling is one of the main initiators of adipogenesis, the conversion from pre-adipocyte to adipocyte or lipid droplet. Rab proteins are the master regulator of intracellular trafficking and endosome fusion in endocytosis, making them potential regulators of insulin signaling in adipogenesis. Pre-adipocytes 3T3-Ll cells expressing several Rab5 constructs were used to examine the effect of dehydroleucodine (DhL ), a sesquiterpene lactone isolated from aerial parts of Artemisia douglasiana Besser. The results obtained identify Rab5 deactivation as a key step for adipogenesis by forming signaling endosomes. The addition of DhL significantly inhibited the lipid droplet accumulation in a dose-dependent manner and dramatically attenuated the synthesis of adipogenic transcriptional factors, C/EBPa and PPARy. Activation of AMPKa, Erk and Akt during adipocytic differentiation was not inhibited by treatment with DhL. This data suggest that DhL has an important role in Rab5 dependent adipogenesis by regulating several transcriptional factors including PP ARy expression, which is known to play an essential role during fat formation.

Natural disaster and household recovery in the aftermath of hurricane Andrew : a case study of four Hispanic households in South Miami Heights

This thesis explores the aid received by four Hispanic households towards recovery after Hurricane Andrew. The four households resided in South Miami Heights, a suburb of Miami. Through the use of questionnaires, information was gathered on various storm related topics. Because the Cuban community in Miami is influential, the role of the Cuban enclave is studied in relation to the recovery of these households. The influence of an urban environment on the extended family ties of these households is also addressed since the literature argues that these ties are powerful among Hispanics. Results show, that aid primarily came from two sources. Furthermore, the Cuban enclave appears to have had no discernible role in the recovery of these households. Finally, an urban setting did not appear to diminish extended family ties.

Natural Disasters and Comparative State-Formation and Nation-Building: Earthquakes in Argentina and Chile (1822-1939)

Natural disasters in Argentina and Chile played a significant role in the state-formation and nation-building process (1822-1939). This dissertation explores state and society responses to earthquakes by studying public and private relief efforts reconstruction plans, crime and disorder, religious interpretations of catastrophes, national and transnational cultures of disaster, science and technology, and popular politics. Although Argentina and Chile share a political border and geological boundary, the two countries provide contrasting examples of state formation. Most disaster relief and reconstruction efforts emanated from the centralized Chilean state in Santiago. In Argentina, provincial officials made the majority of decisions in a catastrophe’s aftermath. Patriotic citizens raised money and collected clothing for survivors that helped to weave divergent regions together into a nation. The shared experience of earthquakes in all regions of Chile created a national disaster culture. Similarly, common disaster experiences, reciprocal relief efforts, and aid commissions linked Chileans with Western Argentine societies and generated a transnational disaster culture. Political leaders viewed reconstruction as opportunities to implement their visions for the nation on the urban landscape. These rebuilding projects threatened existing social hierarchies and often failed to come to fruition. Rebuilding brought new technologies from Europe to the Southern Cone. New building materials and systems, however, had to be adapted to the South American economic and natural environment. In a catastrophe’s aftermath, newspapers projected images of disorder and the authorities feared lawlessness and social unrest. Judicial and criminal records, however, show that crime often decreased after a disaster. Finally, nineteenth-century earthquakes heightened antagonism and conflict between the Catholic Church and the state. Conservative clergy asserted that disasters were divine punishments for the state’s anti-clerical measures and later railed against scientific explanations of earthquakes.

Photo-Reactivity of Natural Dissolved Organic Matter from Fresh to Marine Waters in the Florida Everglades, USA

Natural dissolved organic matter (DOM) is the major absorber of sunlight in most natural waters and a critical component of carbon cycling in aquatic systems. The combined effect of light absorbance properties and related photo-production of reactive species are essential in determining the reactivity of DOM. Optical properties and in particular excitation–emission matrix fluorescence spectroscopy combined with parallel factor analysis (EEM-PARAFAC) have been used increasingly to track sources and fate of DOM. Here we describe studies conducted in water from two estuarine systems in the Florida Everglades, with a salinity gradient of 2 to 37 and dissolved organic carbon concentrations from 19.3 to 5.74 mg C L−1, aimed at assessing how the quantity and quality of DOM is coupled to the formation rates and steady-state concentrations of reactive species including singlet oxygen, hydroxyl radical, and the triplet excited state of DOM. These species were related to optical properties and PARAFAC components of the DOM. The formation rate and steady-state concentration of the carbonate radical was calculated in all samples. The data suggests that formation rates, particularly for singlet oxygen and hydroxyl radicals, are strongly coupled to the abundance of terrestrial humic-like substances. A decrease in singlet oxygen, hydroxyl radical, and carbonate radical formation rates and steady-state concentration along the estuarine salinity gradient was observed as the relative concentration of terrestrial humic-like DOM decreased due to mixing with microbial humic-like and protein-like DOM components, while the formation rate of triplet excited-state DOM did not change. Fluorescent DOM was also found to be more tightly coupled to reactive species generation than chromophoric DOM.