This study covers grafting of Acrylic Acid (AA) and Methacrylic Acid (MAA) on Ultrahigh Molecular Weight Polyethylene (UHMWPE) thin films by surface grafting and xylene-swollen grafting methods with Co-60 &amp / #947 / -ray in air. Also characterizations of pure, irradiated and grafted films were made by applying gravimetric, spectroscopic, thermal and mechanic tests. The thin films of UHMWPE were prepared by using compression molding. AA and MAA grafting on thin UHMWPE films were carried out by surface grafting and xylene-swollen grafting methods. During grafting processes, homopolymerization of monomers was avoided by using Fe2+ and Cu2+ ions. Grafting degree of AA and MAA were calculated for the samples irradiated at different doses. To verify grafting of AA and MAA on UHMWPE films, FTIR spectra of grafted films were used. Metal-uptake capacity is important property of grafted polyethylene for environmental applications. Thus, we examined metal-uptake capacities of AA and MAA grafted films for Fe(III) and Ni (II) and it was found that AA and MAA grafted UHMWPE films showed good affinity towards Fe(III) and Ni(II) metals. Thermal behavior of films were examined by DSC analysis. First run and second run DSC thermograms showed the thermal stability of films under heat. Mechanical properties of UHMWPE decrease with irradiation and grafting. However stress at break values of xylene-swollen grafted samples tend to increase with irradiation dose. In conclusion, water soluble monomers were successfully grafted on UHMWPE and these AA and MAA grafted UHMWPE films can be used in biomedical, environmental applications and other related areas.

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The complex interactions at the interfaces of minerals, microbes, and metals drive the cycling of iron and the fate and transport of metal(loid)s in contaminated systems. The former uranium mine near Ronneburg, Germany is one such system, where slightly acidic mine drainage crossing a steep redox gradient (groundwater outflow into a stream) forms and transforms iron (oxy)hydroxide nanoparticles. These particles interact with toxic metal(loid)s in water and sediments. Iron oxidizing and reducing bacteria also play a role in these processes. Biogeochemical reactions are influenced by nanoscale properties, and thus it is critical to probe environmental samples with appropriate techniques such as analytical transmission electron microscopy (TEM). This dissertation presents two studies on the iron (oxy)hydroxide mineral nanoparticles found in the Ronneburg mine drainage system. The first study uses TEM in conjunction with bulk analytical techniques to demonstrate the complexity of iron (oxy)hydroxide transformations at the steep redox gradient, and the partitioning of metal(loid)s within those mineral phases. An important result was the identification of Zn-bearing green rust platelets in the anoxic outflow water. Green rust minerals have only been identified in nature a handful of times, and we believe this work to be only the second to examine naturally occurring green rust using high resolution TEM (HR-TEM). Downstream of the outflow, aggregates of poorly crystalline iron oxide spheroids co-precipitated with amorphous silica formed and settled to the stream bed, where they aged to form nanoparticulate goethite and sequestered metals such as As and Zn. However, significant concentrations of Zn and Ni remained in the dissolved/nano (< 0.1 um) water fraction and continued downstream. The second study demonstrates that natural green rust nanoparticles and their synthetic analogs can be complex polycrystalline phases composed of crystallites only a few nanometers in size, and often include nano-regions of amorphous material. In addition to the typical pseudo-hexagonal platelet morphology, green rust nanorods were synthesized, which has not previously been reported. This work has important implications for the reactivity of green rust with biogeochemical interfaces in natural, anthropogenic, and industrial systems. A third study, presented in the appendix, characterizes the bacterial community at the Ronneburg mine drainage site and highlights iron oxidizers such as Gallionella sp., in particular those that form stalks of iron oxide nanoparticles. These biogenic stalks also contribute to the uptake of metal contaminants in water and sediments. The science of iron cycling is complex. It requires field-based exploration to enrich the contributions made by experimental, laboratory and modeling studies. This dissertation adds another chapter in the search for filling in missing pieces of this interconnected system. / Ph. D.

Microalgae play a key function in aquatic ecosystems. Their development and growth are strongly regulated by trace metals as essential elements. However, trace metals could cause negative effects when exceeding certain concentrations in the environment. In this study we tested the development and growth rate of two freshwater microalgae, the cyanobacterium Pseudanabeana mucicola and the green alga Pediastrum duplex, from Vietnam over the period of 14 days exposing to chromium (Cr) at the concentrations up to 1,936 μg L-1. Besides, the Cr uptake and absorption by P. mucicola were evaluated over 7 days incubated in medium containing 422 μg Cr L-1. The results showed that Cr at the concentrations up to 1,078 μg L-1 did not inhibit the development and growth rate of P. mucicola. Similarly, concentration of 224 μg Cr L-1 had no adverse effects on growth of P. duplex. The cyanobacterium P. mucicola could make a reduction up to 71% of Cr in the test medium, hence become a distinguished candidate for metal phytoremediation. To the best of our knowledge this is the first investigation on the responses and absorption of Cr by freshwater microalgae from Vietnam. / Vi tảo đóng vai trò quan trọng trong hệ sinh thái thủy vực. Sự sinh trưởng và phát triển của chúng được điều tiết mạnh mẽ bởi kim loại vi lượng như những yếu tố thiết yếu. Tuy nhiên, những kim loại vi lượng này có thể gây ra những ảnh hưởng tiêu cực khi vượt quá nồng độ nhất định trong môi trường. Trong nghiên cứu này, chúng tôi thử nghiệm sự phát triển và tốc độ phát triển của hai loài vi tảo nước ngọt: loài tảo lam Pseudanabeana mucicola và loài tảo lục Pediastrum duplex có nguồn gốc từ Việt Nam trong thời gian 14 ngày phơi nhiễm với crôm (Cr) tại nồng độ lên tới 1.936 μg L-1. Bên cạnh đó, sự hấp thu Cr của P. mucicola cũng đã được đánh giá trong thời gian 7 ngày nuôi trong môi trường chứa 422 μg Cr L-1. Kết quả cho thấy Cr tại nồng độ lên tới 1.078 μg L-1 không kìm hãm sự phát triển và tốc độ sinh trưởng của P. mucicola. Tương tự, tại nồng độ 224 μg Cr L-1 không có bất kì ảnh hưởng tiêu cực đến sự phát triển của P. duplex. Loài tảo lam P. mucicola có thể làm giảm 71% hàm lượng Cr trong môi trường thí nghiệm, vì vậy được xem là ứng viên sáng giá cho quá trình xử lý môi trường ô nhiễm kim loại bằng thực vật . Theo hiểu biết của nhóm tác giả, đây là nghiên cứu đầu tiên về đáp ứng và hấp thu Cr bởi những vi tảo nước ngọt có nguồn gốc từ Việt Nam.

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