[pt] Neste trabalho foi avaliado o potencial do microorganismo R. opacus como biossorvente para a remoção de Pb(II), Cr (III) e Cu(II) de soluções aquosas pelo processo de biossorção/bioflotação, através de ensaios experimentais em batelada. Os parâmetros operacionais investigados na etapa de biossorção foram: o pH da solução, a concentração de biomassa, o tempo de contato e a concentração inicial do metal. Na separação da biomassa carregada mediante a bioflotação por ar disperso se avaliou o tempo de flotação, e as características da espuma. As características da superfície do micro-organismo e os possíveis mecanismos de interação envolvidos na sorção dos metais tóxicos por R. opacus, foram avaliadas com base em medições de potencial zeta, análise por espectrometria no infravermelho e análise de micrografias obtidas no microscópio eletrônico de varredura (MEV). O valor inicial do pH da solução afetou a sorção dos metais, os valores de pH adequados na etapa de sorção e na flotação foram de 5,0 para o Pb(II) e pH igual a 6,0 para o Cr(III) e Cu(II). Os ensaios da cinética de biossorção mostraram que o processo é rápido e em 60 minutos de contato entre a biomassa e a solução de metal foi atingida a máxima captação das espécies metálicas em estudo. Os dados correspondentes à capacidade de captação do R. opacus em função da concentração dos íons metálicos foram bem ajustados ao modelo da isoterma de Langmuir para as três espécies em estudo, onde as capacidades máximas de captação obtidas foram: 94,3; 72,9 e 32,2 mg.g-1 para Pb(II), Cr(III) e Cu(II), respectivamente. A cinética da sorção para o Pb(II), Cr(III) e Cu(II) foram modeladas usando a equação de pseudo segunda ordem. A ordem de afinidade do R. opacus obtida em sistemas individuais foi estabelecida como: Pb(II) >Cr(III)>Cu(II). Essa diferença na afinidade do R. opacus pode ser atribuída às propriedades físico-químicas destes metais, dentre elas peso atômico, raio iônico e eletronegatividade. A capacidade de captação dos íons Pb (II) pela biomassa foi reduzida pela presença de outras espécies metálicas no sistema, apresentando o Cr(III) maior afinidade pelos sítios da biomassa do que os outros íons. Na bioflotação, verificou-se que o micro-organismo apresenta resultados muito promissores como coletor e espumante, obtendo-se percentagens de remoção de Pb(II), Cr(III) e Cu(II) de 94%, 54% e 43% , respectivamente, partindo de uma concentração de 20 mg.l-1. Os resultados apresentados mostram que R. opacus apresenta características adequadas no que tange a biossorção e bioflotação para a remoção de metais pesados. / [en] This work evaluated the potential of the Rhodococcus opacus strain as a biosorbent for the removal of Pb(II), Cr(III) and Cu(II) from aqueous solutions by Biosorption/bioflotation process, through experimental batch tests. The operational parameters investigated in the biosorption´s stage were: pH of the solution, biomass concentration, contact time and initial metal concentration. In the separation of the loaded biomass by bioflotation process for dispersed air were evaluated the flotation time and the foam characteristics. The characteristics of the microorganism surface and the involved interaction mechanisms in the heavy metals sorption by R. opacus, were evaluated based in the potential zeta measurements, infrared spectroscopy and electron microscopy scanning analysis. The solution initial pH value affected metals sorption, the adjusted pH values in the sorption and the flotation stage were 5.0 for the Pb(II) and pH value of 6.0 for the Cr(III) and Cu(II). The experiments of biosorption kinetics showed that the process is relatively fast and in sixty minutes of contact between the biomass and the metal solution were reached the maximum metal uptake capacities. The data pertaining to the uptake capacity of the R. opacus in function of the metal ion concentration fitted to the Langmuir isotherm model for the tree species in study, where the maximum uptake capacities obtained were: 94.3; 72.9 and 32.2 mg.g-1 for Pb (II), Cr(III) and Cu(II), respectively. The kinetics of sorption of Pb(II), Cr(III) and Cu(II) were modeled using a pseudo second order rate equation. The affinity order of R. opacus for the three metals under study has been established as: Pb(II)>Cr(III)>Cu(II). The selectivity of the biomass for the Pb(II) over the other two metals was well exhibited by the results obtained in the biosorption and bioflotation. This difference in the affinity of the R. opacus can be attributed to the physiochemical properties of these metals, amongst them atomic weight, ionic radio and electronegativity. The uptake capacity of ions Pb(II) for the biomass was reduced by the presence of other metallic species in the system, and the results showed that the Cr(III) has greater affinity for the biomass than the others ions. In the bioflotation, it was found that the microorganism presents excellent characteristics as collector and foaming agent, reaching 94%, 54% and 43% removal of lead, chromium and copper, respectively, to 20 mg.l-1 of concentration. The results of this study showed that R. opacus has important features for the heavy metal removal; moreover, the results also showed that R. opacus is especially effective biosorbent for the removal of Pb(II).

In order to keep global average temperature below 2°C it is necessary to accelerate climate change mitigation actions and reduce global greenhouse gas emissions. This can be achieved by carbon capture and storage methods such as the production of biochar. Especially its production from municipal sewage sludge could decrease emissions and disposal costs as well as act as a valuable material for different fields of application afterwards. In this quantitative study, the potential for a biochar production system was investigated for the case of the Swedish island, Gotland. Documents and grey literature were reviewed to collect the necessary information and data and experts were asked to fill in information gaps to evaluate the following: Calculate the energy and mass balance of a biochar production system from municipal sewage sludge in 2018, to find possible applications for the produced biochar by investigating the heavy metal content as well as to assess the direct carbon sequestration potential of the produced biochar. The results indicate that in 2018, 540 t of biochar could have been produced with a net heat demand of around 543 MWhth and electricity consumption of 231 MWhel. Heavy metal contents were found to be very high especially for copper and zinc, which means that the produced biochar would only qualify for the EBC-BasicMaterial certification class of the European Biochar Certificate. The annual carbon sequestration potential resulted in 97.2 t of carbon stored in the material or 356.4 t of CO2 emissions saved. Further research needs to be conducted on economic factors of a biochar production system from municipal sewage sludge.

Packaging Materials account for 31% of the world’s municipal solid waste. Agencies like the Environmental Protection Agency (EPA) and the Agency for Toxic Substances and Disease Registry (ATSDR) are pushing for the increased use of recycled thermoplastic materials. Polyethylene terephthalate (PET) is a commonly recycled thermoplastic which is used to package ready-to-eat fruits and vegetables. Most recycled polyethylene terephthalate (RPET) packaging materials contain heavy metal catalysts, the most common being antimony. The recent increased use of recycled plastic materials has been suspected as the source of increased human heavy metal exposure. In this study, cadmium, chromium, nickel, lead and antimony were quantified in post-consumer RPET rigid containers and films using inductively coupled plasma-atomic emission spectrometry (ICP-AES). Two hundred samples were tested of which 29 were found to be contaminated with heavy metals in the parts-per-million (ppm) range. Chromium was found in all the contaminated sample replicates at an average level of 8.18 ppm. Cadmium was found in all the contaminated samples as well. Lead was found in 90.4% of the contaminated samples and concentrations ranged from a low of 0.02 ppm to a high of 0.36 ppm. Nickel was found in 96.4% of the contaminated samples while antimony was found in 97.6% of the samples. Due to limited sample material, 22 of the 29 contaminated RPET rigid containers and films were tested for heavy metal migration into a 5% citric acid:water solution (w/v) or deionized water. Samples were subjected to prolonged storage at 7.2 or 22.2°C for 1, 7 or 14 days, or were exposed for 5 minutes to microwaves from a 1700-watt microwave oven set to 70% power before analysis. Leachate values were at ppb levels but were often below the ICP-AES Limits of Detection which were at also the ppb level, whether calculated for deionized water or 5% citric acid in water. No measureable levels of heavy metal were detected for any sample exposed to water, regardless of treatment. For samples exposed to 5% citrate and stored or microwaved, only chromium and nickel leached at measurable levels, and the number of RPET’s releasing measurable chromium and nickel increased with microwaving compared to the same plastics stored at 22.2 or 7.2°C. Since leaching was calculated as µg/L of heavy metal lost from the entire inner surface (1021 cm2) of a retail salad bag, actual exposure to heavy metal would be much less than measured in this study as retail fruit and vegetable packages and microwaveable pouches usually contain very little liquid in order to increase food safety. The results therefore suggest the potential for little migration of heavy metal from recycled PET to whole or fresh-cut fruits and vegetables when held at ambient or refrigerated temperatures, or when microwaved.

京都大学 / 新制・課程博士 / 博士(工学) / 甲第23870号 / 工博第4957号 / 新制||工||1774(附属図書館) / 京都大学大学院工学研究科都市環境工学専攻 / (主査)教授 高岡 昌輝, 教授 藤原 拓, 准教授 大下 和徹 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

In the Saudi Arabian Red Sea, two of the seven species of sea turtles are known to nest and forage along the coast, the hawksbill turtle (Eretmochelys imbricata) and the green turtle (Chelonia mydas). As a result of some life history characteristics, sea turtles are particularly vulnerable to anthropogenic impacts. Under Saudi Arabia’s Vision 2030 and the recent opening of its borders to recreational tourists, the country aims to develop several large-scale projects along the Red Sea coast, locally known as “giga-projects”. Thus, imminent pressures from coastal development highlight the urgency needed for multi-country cooperation in protecting sea turtles in the region. This dissertation aims to establish some baseline data and protocols for future work to meet the data needs of the relevant conservation authorities in Saudi Arabia. In particular, this thesis contributes new and important information to some of the identified knowledge gaps for the Red Sea region, including sea turtle habitat use, threat assessment (plastic and heavy metal pollution), and evaluating hatching success. I used satellite telemetry to understand foraging home ranges of hawksbill and green turtles, post-nesting migrations, and inter-nesting habitat use of green turtles. Additionally, I used photo identification to understand the abundance and behavior of turtles at a Rabigh fringing reef, in the central Red Sea. I assessed two anthropogenic contaminants as a threat to Red Sea turtles: heavy metal contamination and plastic ingestion. Heavy metal concentrations in the sand were evaluated at the largest green turtle rookery in Saudi Arabia, Ras Baridi, which is located next to a cement factory. I also assessed the concentration of heavy metals in the tissues of dead hatchlings found at Ras Baridi. Additionally, I studied plastic ingestion in ten deceased turtles found along the Saudi Arabian Red Sea. In my last data chapter, I assessed the hatching success of green turtle nests, and investigated clutch relocation as a possible method of increasing success. The final chapter summarizes the results from this research in the context of the 2004 PERSGA Marine Turtle Conservation Plan, and provides possible conservation strategy recommendations to protect Red Sea turtles

Surges of Sargassum have become more severe and at the time of writing the largest surge yet is set to hit the Caribbean islands, affecting tourism and marine life negatively. Tourism is Grenada’s single handedly largest economic sector, which is why it is important to research the use of Sargassum. Furthermore, for its fertiliser needs, Grenada relies largely on importing inorganic fertiliser, which has become more expensive in recent years. Sargassum as feedstock for biogas digesters and utilising the digestate as fertiliser could be a viable option, but challenges include high heavy metal content and low concentration of nutrients compared to inorganic fertiliser. The aim of this project is to examine heavy metals contents in digestate derived from Sargassum and gaining knowledge about the current agricultural situation, with regards to fertiliser, through interviewing farmers and relevant political figures. The results from the heavy metal analysis of the liquid digestate showed that the concentration of both arsenic and cadmium were below the average for commercial organic fertilisers. However, further testing is considered to be required to conclude whether the product is suitable to use. Gathered from the interviews was that many farmers were concerned about the impact inorganic fertiliser had on the land, however, the choice of fertiliser was, in general heavily dependent on which type was available. Sargassum-based digestate could be viable on the island but challenges of reducing, transporting and separating heavy metals from the digestate have to be solved making it difficult for the Sargassum to be cost-effective. Furthermore, the farmers were very clear that they wanted a product which was safe to use. / Sargassumblomningar har blivit allvarligare och i skrivande stund väntas den största vågen hittills att drabba de karibiska öarna, vilket har en negativ påverkan på turismen och det marina livet. Turismen är Grenadas enskilt största ekonomiska sektor, och därför är det viktigt att undersöka användningsområdet för Sargassum. Dessutom är Grenada, för sitt gödselbehov, till stor del beroende av import av oorganiskt gödningsmedel, vilket har ökat i pris de senaste åren. Sargassum som inmatning för biogasrötningsanläggningar och användning av rötrester som gödningsmedel skulle kunna vara ett lönsamt alternativ, men utmaningarna är bland annat det höga innehållet av tungmetaller och den låga koncentrationen av näringsämnen jämfört med oorganiska gödningsmedel. Syftet med detta projekt är att undersöka innehållet av tungmetaller i digestat från Sargassum och att få kunskap om den nuvarande jordbrukssituationen gällande gödningsmedel genom att intervjua jordbrukare och relevanta politiker. Resultatet av den tungmetallanalys som genomfördes av det vätskeformiga digestatet visade ett innehåll av kadmium och arsenik som låg under medelvärdet för kommersiella organiska gödningsmedel. Däremot är vidare testning är nödvändig för att säkerställa att produkten är lämplig att använda. Intervjustudien visade att många jordbrukare var oroade över hur oorganiska gödselmedel påverkar marken, men att valet av gödselmedel i allmänhet var starkt beroende av vilken typ av gödningsmedel som fanns tillgängligt. Sargassumbaserat digestat skulle kunna vara lönsamt för användning på ön, men problemen med reducering, transport och separering av tungmetaller från digestatet måste lösas, vilket gör det svårt för Sargassum att vara kostnadseffektivt. Bönderna var slutligen tydliga med att digestatet från Sargassum behövde generera en ökning eller likvärdig produktion av deras grödor.

Phytoremediation has been intensively studied during the past decade due to its cost-effectiveness and environmental harmonies. Most of the studies on treatment of heavy metal pollution in soil and water by plant species have been done in developed countries but are limited in Vietnam. In this study, we presented some research results of phytoremediation of polluted soils and water with heavy metals that were done by Institute of Environmental Technology for several last years. For treatment of heavy metal pollution in the water, some plants have great ability to accumulate heavy metals such as Vetiveria zizanioides, Phragmites australis, Eichhornia crassipes, Pistia stratiotes, Ipomoea aquatica, Nypa fruticans and Enhydra fluctuans. The heavy metal uptake into shoots and roots of 33 indigenous plant species in Thai Nguyen province was also determined. Two species of the plants investigated, Pteris vittata L. and Pityrogramma calomelanos L. were As hyperaccumulators, containing more than 0.1% As in their shoots while Eleusine indica, Cynodon dactylon, Cyperus rotundus and Equisetum ramosissimum accumulated very high Pb (0.15-0.65%) and Zn (0.22-1.56%) concentrations in their roots. Some experiments to clarify the potential of several plants as good candidates for phytoremediation of polluted soil by heavy metals were carried out in our institute. / Phương pháp sử dụng thực vật để xử lý ô nhiễm đã được nghiên cứu nhiều trong thập kỷ qua do chi phí thấp và thân thiện với môi trường. Hầu hết các nghiên cứu về xử lý ô nhiễm kim loại nặng trong đất và nước bằng thực vật đã được thực hiện ở các nước phát triển nhưng ít có tại Việt Nam. Trong nghiên cứu này, chúng tôi giới thiệu một số kết quả dùng công nghệ thực vật để xử lý ô nhiễm kim loại nặng trong đất và nước tại Viện Công nghệ môi trường trong những năm gần đây. Dối với xử lý ô nhiễm kim loại nặng trong nước, một số thực vật có khả năng tích lũy tốt kim loại nặng như Vetiveria zizanioides, Phragmites australis, Eichhornia crassipes, Pistia stratiotes, Ipomoea aquatica, Nypa fruticans và Enhydra fluctuans. Sự hấp thụ và tích lũy kim loại nặng trong phần trên mặt đất và rễ của 33 loài thực vật bản địa tại Thái Nguyên cũng đã được xác định. Hai loài thực vật khảo sát là Pteris vittata và Pityrogramma calomelanos là những loài siêu tích lũy As, chứa hơn 0,1% As trong phần trên mặt đất của cây. leusine indica, Cynodon dactylon, Cyperus rotundus và Equisetum ramosissimum tích lũy Pb (0,15-0,65%) và Zn (0,22-1,56%) rất cao trong rễ. Một số thí nghiệm đánh giá tiềm năng của một số thực vật là đối tượng tốt cho xử lý ô nhiễm kim loại nặng trong đất đã được tiến hành trong phòng thí nghiệm của Viện Công nghệ môi trường.

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