Rozprawy doktorskie na temat „Toxic Heavy Metals - Waste Water”

In this research, it is aimed to remove toxic heavy metals in waste water with the help of fly ash from Ç
ayirhan thermal power plant. The chemical and physical properties (size distribution, specific surface area, porosity, chemical composition, etc.) of fly ash were determined. The experiments were carried out in synthetic waste water containing lead, zinc and copper metals at different concentrations with the addition of fly ash. The effects of metal concentration, agitation time, particle size, ash amount, and pH in the metal removal were examined. With the addition of even very small amount of fly ash, heavy metal removal from waste water was attained at up to 99%. Fly ash particle size has no significant effect on removal of heavy metal ions from solutions. Higher solution pH and longer treatment time were resulted better metal removal. The results also indicated that the main mechanism for metal removal was precipitation due to alkaline characteristics of fly ash and more than 90 % of metals in solutions were removed by precipitation. The pH ranges for maximum metal precipitation were 10-11, 8-10, and 10-11 for copper, zinc, and lead respectively. Very small percentages of adsorbed metal was released during the desorption test.

The thesis presents the development of polymer based electrospun nanofibers as diagnostic probes for the selective detection of toxic metal ions in water. Through modification of the chemical characteristics of nanofibers by pre- and post-electrospinning treatments, three different diagnostic probes were successfully developed. These were the fluorescent pyridylazo-2-naphthol-poly(acrylic acid) nanofiber probe, the colorimetric probe based on glutathione-stabilized silver/copper alloy nanoparticles and the colorimetric probe based on 2-(2’-Pyridyl)-imidazole functionalized nanofibers. The probes were characterized by Fourier transform infrared spectroscopy (FTIR), Energy dispersive x-ray spectroscopy (EDX), Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The fluorescent nanofiber probe was developed towards the determination of Ni²⁺. Covalently functionalized pyridylazo-2-naphthol-poly(acrylic acid) polymeric nanofibers were employed. The solid state Ni²⁺ probe exhibited a good correlation between the fluorescence intensity and nickel concentration up to 1.0 mg/mL based on the Stern-Volmer mechanism. The detection limit of the nanofiber probe was found to be 0.07 ng/mL. The versatility of the fluorescent probe was demonstrated by affording a simple, rapid and selective detection of Ni²⁺ in the presence of other competing metal ions by direct analysis without employing any sample handling steps. For the second part of the study, a simple strategy based on the in-situ synthesis of the glutathione stabilized silver/copper alloy nanoparticles (Ag/Cu alloy NPs) in nylon 6 provided a fast procedure for fabricating a colorimetric probe for the detection of Ni²⁺ in water samples. The electrospun nanofiber composites responded to Ni²⁺ ions but did not suffer any interference from the other metal ions. The effect of Ni²⁺ concentration on the nanocomposite fibers was considered and the “eye-ball” limit of detection was found to be 5.8 μg/mL. Lastly, the third probe was developed by covalently linking an imidazole derivative; 2-(2′-Pyridyl)-imidazole (PIMH) to Poly(vinylbenzyl chloride) (PVBC) and nylon 6 nanofibers by post-electrospinning treatments using a wet chemical method and graft copolymerization technique, respectively. The post-electrospinning modifications of the nanofibers were achieved without altering their fibrous morphology. The color change to red-orange in the presence of Fe²⁺ for both the grafted nylon 6 (white) and the chemically modified PVBC (yellow) nanofibers was instantaneous. The developed diagnostic probes exhibited the desired selectivity towards the targeted metal ions.

Water is an essential element in all aspects of life and is vital for both domestic and industrial purposes regarding both the quality and quantity thereof. Similar to many other drought stricken countries, South Africa requires water for the socio-economic growth of the country, yet is faced with the problem of maintaining the quality of its drinking water as well as protecting the dwindling supplies. In an attempt to prevent the deterioration of South African water supplies the treatment, purification and recycling of industrial and mining waste water has recently become of prime importance. Many industrial and mining waste waters contain heavy metals in toxic quantities. The conventional processes that have been used till recently to address this problem, are often expensive or contain chemical agents which compound the environmental problem. As an alternative biological methods of metal accumulation appear to offer an economic and efficient alternative to these methods. An advantage to the South African scenario is the commercial production of the yeast, S. cerevisiae as a readily inexpensive by-product from some fermentation industries, Yeast cells, and in particular S. cerevisiae have proven to be capable of accumulating heavy metals, and therefore exhibit potential application in the bioremediation of waste water. The aim of this project was twofold. The initial part of this work attempted to define the mechanisms of metal accumulation by the yeast cells and cellular components. The information obtained from these initial studies provided a data base required for the development of a bioremediation system. Initial contact with the metal ions occurs at the wall interface of the yeast cell. Metal accumulation appears to be a function of all the cell wall components. The isolated cell wall components are better metal chelators then the intact cell walls. An apparent affinity series of mannan > chitin> glucan > intact cell walls exists. However, these components differ in their affinities for metal ions. Storage of metal ions within the cell occurs predominantly in the vacuole. The present study concluded that metal accumulation by the vacuole could be related to size. Metal accumulation occurred in the order of Cu2+ > Co2+ > Cd2+ with a corresponding decrease in atomic radii of Cd2+ > C02+ > Cu2+. Vacuolar ion deposition occurs at an early stage during the internalization of metal ions within the yeast cells. At the onset of vacuolar saturation, depositions of metal ions as granules within the cytosol occurs. In the presence of heavy metal cations viable yeast cells can be shown to exhibit two types of cellular responses. Uptake of Cu2+ and Cd2+ causes the loss of intracellular physiological cations from within the yeast cell. In comparison, uptake of Co2+ into the cell does not have this effect. All three heavy metal cations initiate plasma cell membrane permeability, thus the Cu2+ and Cd2+ induced loss of the intracellular cations, occurs. ~ a result of ion-exchange mechanisms and not due to cation leakage brought about by membrane permeabilization. Uptake of heavy metals by viable yeasts appears to be generally non-selective though the amount of metals accumulated are largely affected by the ratio of ambient metal concentration to biomass quantity. In addition, the energy dependent nature of internalization necessitates the availability of an external energy source for metal uptake by viable yeast cells. For these reasons metal removal from industrial waste water was investigated using non-viable biomass. By immobilizing the yeast cells additional mechanical integrity and stability was conferred apon the biomass. The three types of biomass preparations developed in this study, viz. polyvinyl alcohol (PV A) Na-alginate, PV A Na-orthophosphate and alkali treated polyethylenimine (PEI):glutaraldehyde (GA) biomass pellets, all fulfilled the necessary physical requirements. However, the superior metal accumulating properties of the PEI:GA biomass determined its selection as a biosorbent for bioremediation purposes. Biosorption of heavy metals by PEI:GA biomass is of a competitive nature, with the amount of metal accumulated influenced by the availability of the metal ions. This availability is largely determined by the solution pH. At low pH values the affinity of the biomass for metals decreases, whilst enhanced metal biosorption occurs at higher pHs, ego pH 4.5 - 6.0. PEI:GA biomass pellets can be implemented -as a biosorbent for the bi9remediaiton of high concentration, low-volume metal containing industrial waste. Several options regarding the bioremediation system are available. Depending on the concentration of the metals in the effluent, the bioremediation process can either be used independently or as part of a biphasic remediation system for the treatment of waste water. Initial phase chemical modification may be required, whilst two types of biological systems can be implemented as 'part of the second phase. The PEI:GA biomass can either be contained within continuous-flow fixed bed tanks or continuous-flow stirred bioreactor tanks. Due to the simplicity of the process and the ease with which scale-up is facilitated, the second type of system shows greater application potential for the treatment of this type of industrial waste water than the fixed-bed systems.

In this thesis, treating portable water from hazardous pollutants such as dyes were studied by preparing TiO2/ZSM-5 mesoporous and modified RGO/TiO2/ZSM-5 mesoporous. Additionally, novel optical conjugated mesoporous adsorbents were prepared to treat portable water from heavy metal ions such as Hg2+ and Pb2+. Results show significant improvement over previous efforts by researchers. The work presented here has profound implications for future studies of wastewater treatment, and may one day help solve the problem of water scarcity.

The aim of this study was to make an inventory of the open dumping site Jhumjhumpur in Jessore, Bangladesh, in order to investigate whether spreading of heavy metals had occurred to surrounding soil and groundwater. The study is based on a thorough literature study as well as a field study, including soil and groundwater sampling, at the dumping site Jhumjhumpur. The literature study covers the current waste management system in three cities of Bangladesh: Dhaka, Jessore and Khulna. The results from the field study indicate that metals from the dumping site have been transported and spread to the groundwater in connection to the site and the agricultural land south of the site. A more complete investigation is needed to be able to determine how big a risk the open dumping site is for the surrounding environment. Measurements for avoiding further contamination of the groundwater and the agricultural land should be implemented.

Zeolites are well-known aluminosilicate minerals that have been widely used as adsorbents in separation, purification processes and environmental pollution control. Zeolites are used in various industrial applications due to their high cation-exchange ability, molecular sieve and cataltic properties. In order to reduce the costs of acquisition and minimise the disposal of adsorbents, both modified natural zeolite and synthetic zeolite (derived from kaolinite) were used for the purification of wastewater. The characteristic properties and applications of adsorbents are also discussed including the advantages and disadvantages of each technique. The present work involves the study of the removal of Cu2+, Fe3+, Pb2+ and Zn2+ from synthetic metal solutions using natural zeolite. Laboratory experiments were used to investigate the efficiency of adsorbents in the uptake of heavy metals from industrial wastewater. These include equilibrium tests, kinetic studies and regeneration studies. The physical and chemical characterization of the zeolites was carried out using different analytical techniques such as Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), X - Ray Diffraction (XRD), X - Ray Fluorescence (XRF), Thermogravimetric Analysis (TGA), Fourier Transform Infrared (FT-IR) Spectroscopy and Inductively Coupled Plasma-Optical Emission Spectrometer (ICP-OES). The kinetic study indicated the suitability of the natural zeolite for the removal of Cu2+, Fe3+, Pb2+ and Zn2+ ions from synthetic wastewater. Batch experiments were used to identify the effect of parameters that affect the rate of adsorption such as the effect of adsorbent mass, effect of adsorbent particle size, effect of initial solution pH, effect of initial solution concentration, effect of agitation speed and effect of pre-treatment of adsorbent and evaluated their impact on the efficiency of the zeolite in the removal of heavy metals from industrial wastewater. The kinetic studies showed that the capacity of the adsorbents for the removal of heavy metals increased with a greater mass of absorbent, increased initial solution pH, increased agitation speed, higher solution concentration as well as the application of a pre-treatment. The results from the equilibrium studies positively demonstrated that natural zeolite can be used as an excellent adsorbent for removing heavy metals from multi-component solutions. The equilibrium experiments indicated that the capacities of natural zeolite for the uptake of heavy metals increased when the initial solution pH increased. The results indicated that the maximum removal capacities Q were 22.83, 14.92, 14.49 and 17.54 mg/g natural zeolite for copper, iron, zinc, and lead respectively. Both the Langmuir and Freundlich isotherm models were used to characterize the experimental data and to assess the adsorption behaviour of natural zeolite for copper, iron, lead and zinc. The experimental data were slightly better suited to the Langmuir isotherm than the Freundlinch isotherm. The value of the correlation coefficients r2 ranged from 0.93 to 0.99 for the Langmuir isotherm and from 0.90 to 0.99 for the Freundlich isotherm. The present work also involved the study of synthetic zeolite A, which was derived from natural kaolinite. The conversion of the raw materials into zeolitic materials was carried out in two ways: first, conventional hydrothermal synthesis and second, alkaline fusion prior to hydrothermal synthesis. The results from both routes show that zeolite A was synthesised successfully. Finally, the experiments show that both natural and synthetic zeolites can be available in commercial quantities. Synthetic zeolites are more attractive for some specific applications, while the cheapness of natural zeolite may favour its use.

Major impacts of current and pre-regulatory mining activities on the environment include the generation of acid mine drainage (AMD) and metal(loid)-laden acid sulfate soils. Current remediation techniques are mostly cost prohibitive due to high energy, material, and labor requirement. This study investigated two complementary low-cost methods that harnessed the metal(loid)-removing and acid-neutralizing properties of drinking water treatment residuals (WTRs) and the uptake (phytoremediation) potential of vetiver (Vetiviera zizanioides L.) and pokeweed (Phytolacca americana L.) to attenuate and immobilize metal(loid)s from natural AMD and metal(loid)-contaminated soil. Metals were removed from AMD by using a reverse flow fluidized column filter and hydroponic phytoremediation with vetiver and pokeweed. Metals were immobilized in soil through the amendment with Fe and Ca-WTR complimented by the uptake and translocation of metals by vetiver and pokeweed. Experiments were performed under controlled greenhouse conditions as well as under natural Illinois environment in simulated field conditions. Furthermore, the integrated effects of WTR application and the growth of vetiver on soil erosion were also studied. Physicochemical analysis of AMD and soil samples from the Tab-Simco abandoned mine in the Illinois Coal Basin, U.S.A, showed significant concentrations of major metals and metalloids such as Fe, Al, Mn, Zn, Ni, Cu and As at acidic pH levels. The degree of soil contamination at the site was spatially variable with respect to the location of the main AMD seep. Physical, chemical, agronomic and mineralogical characterization of locally acquired water treatment residuals (WTR) showed that the silty and alkaline (pH ≈ 7.0-9.1) materials also contained significant amounts of plant required micronutrients. The presence of amorphous phases of mostly metal (oxy)hydroxides, alkalinity, and porosity of the WTRs suggested the potential to neutralize acidity and capability to remove metal(loid)s in contaminated soils and AMD. Recorded metal removal (%MR) rate by WTR was rapid in the first 80 min in a batch agitation study, except for Mn. Thus, high metal removal ranging from 99.8% to 84.9% at selectivity sequence of Al>Fe>Cu>Zn and Mn (9.6%) was obtained at equilibrium. The pH of the AMD was also increased from 2.6 to 6.7. Analysis of leachate samples from gravity-drained columns following simulated rain events in a greenhouse study showed reduced concentrations of Al, Fe, Mn, Zn, Cu, As and Pb at sustained neutral pH compared with unamended control columns during the 12 weeks study period. Metal immobilization in soil by the lower amendment rates of WTR was comparable to the higher application rates and also showed lower oxalate extractability of metals. Tissue analysis of pokeweed and vetiver hyperaccumulators showed appreciable uptake of relevant elements although translocation was relatively low in both. The analytical results at the greenhouse scale was reproducible in a simulated field scale study under natural Illinois environmental condition where the best amendment rate including 50 g/kg Fe-WTR and 15 g/kg of Ca-WTR and manure helped to improve metal(loid) retention, soil structure and enhanced vetiver growth which subsequently aided in reducing the rate of erosion to levels comparable to bermudagrass which was used as control. The developed integrated WTR fluidized column and phytoremediation technique with vetiver and pokeweed under hydroponic conditions sequentially removed significant quantities of most heavy metals from AMD. Thus, the overall findings showed that the locally collected WTRs - the otherwise waste materials, showed high metal-removing and acidity-reducing capabilities in AMD and contaminated soil treatment applications. The similarity between the results obtained from the laboratory and simulated field study also showed that laboratory/greenhouse experiments may serve as reliable proxies for field responses in applications such as soil and water conservation in agricultural environments, remediation of abandoned mine lands, as well as wastewater treatment systems.

Ensåsengruvan is a mine situated within Ljusdals municipality in central Sweden. Themine was in use from 1984 to 1991 and has since been undergoing a remediation program. Mine tailings from sulfide rich ore is a potential environmental hazard due to its tendency to cause acid waters and heavy metal leakage. Lake Ensjön is situated one kilometer from the mine area. Due to the hydrological conditions it was not expected to receive inflowing water from the mining area. A study done in 2005 showed high amounts of heavy metals in the lake.

In this study water and sediments was analyzed to confirm the results from the 2005 study. Water was sampled two times during summer 2006 from the lake and adjoining streams. Sediment samples were collected with a core sampler at ten different locations within the lake. The water and sediment samples were analyzed for heavy metal content. Sub-samples from different depths in the sediment core were extracted so that conclusions on the contamination history could be drawn. The sediments were dated trough Cs-137 analyses. The depth in the profile with the highest Cs-137 content can be dated to the time of the Chernobyl fallout (1986). After dating, relevant samples were analyzed for metal content.

The results show that Ensjön is contaminated by a local source. The surface sediments are high in copper, zinc, nickel and cadmium content. The content is high both compared to the samples from deeper in the sediment core and the surface sediments analyzed in the reference study done in 1980. The amounts of heavy metals are also high relative to the standards set by the Swedish Environmental Protection Agency. The water from the stream adjoining the lake from the mining area is high in content of the previously mentioned metals. The methods used, including sediment dating and metal analyses together with water analyses, has proven to be useful in investigating a suspected contamination from a point source.

It can be concluded that Lake Ensjön is contaminated with water from the mine waste. No other sources in the catchment area can be the source of the enriched amounts of heavy metals. Focus should in further work be put upon finding the exact source of leakage from the mining area.

Från Enåsengruvan i Ljusdals kommun utvanns ur sulfidmalm guld, silver och koppar under åren 1984 till 1991. Avfall från sulfidmalmsgruvor medför miljöproblem genom försurning och läckage av tungmetaller. Vanligtvis täcks avfallet med jordmassor eller vatten för att förhindra påverkan på naturen. De studier som genomfördes under prospekteringen visade på att Ensjön, som är belägen inom en kilometers avstånd från gruvområdet, inte skulle påverkas av gruvan men en provtagning under 2005 visade på höga halter av tungmetaller i sjön.

I denna studie har Ensjöns vattenkvalitet undersökts genom vatten och sedimentanalyser. Vattenprover i sjön och dess inlopp togs två gånger under sommaren 2006 och sedimentprover togs vid ett tillfälle på tio olika lokaler i sjön. En djupprofil av sedimenten analyserades för att föroreningshistoriken från innan gruvan togs i bruk till nutid skulle kunna kartläggas. För att datera sedimenten analyserades de med avseende på Cs-137. De högsta halterna av Cs-137 kan härledas till nedfallet från Tjernobylolyckan 1986. Efter datering valdes lämpliga prover ut för metallanalys.

Resultaten visar på förhöjda halter av koppar, zink, nickel och kadmium. Halterna i ytsedimenten är höga både jämfört med de halter som återfinns på större djup i sedimentprofilen, motsvarande avsättning innan gruvdriften och vad som uppmättes i referensstudien från 1980. Halterna är även höga relativt de jämförvärden som Naturvårdsverket satt upp. Vattenanalyserna visar på att vattnet i inflödet från gruvområdet innehåller höga halter av de tidigare nämnda metallerna. Metoden med Cs-137-datering och analys med avseende på metaller av sediment har visat sig fungera väl för kartläggning av en nutida förorening från en punktkälla. Tillsammans med kompletterande vattenprover ger det en bra bild av den rådande situationen.

Då resultaten visar att Ensjöns vatten är påverkat av en punktkälla och alla andra källor kan uteslutas får det anses klarlagt att sjöns vatten är påverkat av dränagevatten från gruvområdet. Fortsatta studier bör fokusera på att klarlägga den exakta källan till läckaget från gruvområdet.

Industriell vattenrening är ett extremt viktigt område inom Miljöskyddsteknik då 60% av allt sötvatten inom Sverige används av industrier. Substanser som PFAS, aromatiska textilfärger, fenol och läkemedelsrester är extra utmanande då dessa kan vara gifta för biologisk rening. Syftet med denna rapport var att först redogöra några av de viktigaste avvägningarna som behöver göras när ett industriellt vattenreningsverk designas. I del två av arbetet har en kartläggning av teknologier som kan användas för att assistera eller ersätta biologisk rening. Det existerar flera olika typer av tekniker för att ersätta biologisk rening, men majoriteten av dessa konsumerar stora mängder värme eller elektricitet, vilket kan leda till stora rörliga kostnader. En trend inom industriell vattenrening är elektrifiering. Elektrifiering ger möjlighet att återvinna kemikalier, selektiv separation av joner, automatisk justering av pH via tekniker som elektrodialys och elektrokoagulering. Kall plasmaoxidation och kavitation kan även användas för destruktion av organiska ämnen. I takt med att förnyelsebar energi blir billigare att producera och om regeringen inför el-subventioner för industrin så kommer användbarheten av dessa tekniker att öka. Membranprocesser kan användas för att intensifiera processer som extraktion och indunstning. Med hjälp av membran kan separationshastigheten och energianvändningen minskas. Enzym kan användas för att skräddarsy rening för att bryta ner specifika ämnen vid låga tryck och temperaturer. Skumseparation är en mycket lovande process som kan användas för separation av ytaktiva ämnen som PFAS och har en mycket enkel design och låga energikostnader.
Industrial water treatment is an important field of study as industries in Sweden consumes over 60% of the available freshwater. Furthermore, only 60% of the industrial wastewater in Europe receive treatment before its discharged. Hard to oxidize compounds such as dyes, phenol, and PFAS are a major problem within the field as they often exhibit toxic or inhibiting qualities towards biological treatment methods. Therefore, the purpose of this thesis is twofold; firstly, some of the most important considerations when designing an industrial wastewater treatment plant is discussed to aid someone new to the field. Secondly, novel technologies that could be used to support or replace biological treatment methods are discussed. There exist several different novel technologies that can be used to treat organic pollutants. However, many of these techniques are very energy intensive, leading to high operational costs. A major trend within wastewater treatment is the electrification of treatment techniques. These enables the recycling of chemicals, selective removal of ions and automatic neutralization of pH by means of electrodialysis and electrocoagulation. They can also be used for destruction of organics using cavitation or cold plasma oxidation. The usefulness of these techniques is likely to increase in the future as the electrification of industry picks up speed and subsidies on industrial electricity prices are put in place. Membrane processes can intensify already existing unit operations such as evaporation and extraction. By employing a membrane, the speed of separation and the energy use can be lowered. Enzymatic treatment can be used to degrade several different compounds at low temperatures and pressures by tailoring the mix of enzymes to perfectly fit the wastewater in question. Foam separation is also interesting technology in the removal of surface-active chemicals and compounds due to its simplistic design and low operational cost. The use of this technology is likely to increase in the future if the legislation regarding persistent organics is tightened further.

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2016-12-22T12:01:06Z No. of bitstreams: 0
Made available in DSpace on 2016-12-22T12:01:06Z (GMT). No. of bitstreams: 0
Os cosméticos labiais estão envolvidos em duas importantes discussões: os problemas de saúde pública e os problemas ambientais. A partir dessas informações, pretende-se analisar qual o impacto na saúde humana, verificar se há relação entre preço, duração e cor e investigar quais os prováveis impactos para o meio ambiente, supondo algumas vias de descarte. Os cosméticos analisados foram batons, divididos por marca, preço e cor. A primeira análise foi por fluorescência de raios-x (FRX). Em seguida, as matérias primas passaram por digestão com ácido nítrico e clorídrico sob aquecimento e foram diluídas com água destilada e filtradas. A seguir, foram realizadas leituras por espectrometria de emissão óptica com plasma indutivamente acoplado (ICP-OES). A partir dos resultados da análise por FRX (foram encontrados 18 elementos metálicos) e a matriz para análise por ICP-OES foi composta por: alumínio, cálcio, cádmio, cobalto, cromo, cobre, ferro, potássio, manganês, níquel, chumbo, silício e titânio. Apesar de terem sido identificados metais tóxicos (Ni, Mn, Cd e Cr) nas amostras, os batons analisados cumprem com o requerido pela legislação nacional em relação aos limites impostos para metais pesados (Pb, Cd, Ni, Cr e Mn) em cosméticos e alimentos. Entretanto, é importante destacar que as legislações cosmética e alimentícia possuem grandes diferenças quanto aos limites impostos para metais pesados. O estudo do descarte dos batons mostrou que mesmo os batons que são mais utilizados, há um desperdício de quase 1/3 do produto por conta da embalagem interna. Essa informação pode auxiliar em um consumo consciente dos batons, tanto para a quantidade desperdiçada, quanto ao risco associado à utilização de um conjunto de maquiagens (bases, sombras, rímel, blush e batom) com outros cosméticos (cremes, perfumes, esmaltes, tintas para cabelo). Risco esse, associado a possíveis problemas à saúde.
Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior
The issue involving the proper management of municipal solid waste is still a serious problem that affects mainly developing countries, just as Brazil. Only in 2010, with the implementation of the National Solid Waste Policy from the Federal Law No 12.305, this issue began to gain traction in the social and economic environment. In this law one of the proposals is the removal and recovery inappropriate sites for the disposal of municipal waste. The adverse consequences of waste disposal involve two fundamental issues, regarding the contaminants migration and another that deals with the sites stability used for their disposal. Therefore, this study aimed to analyze the support of the geological environment for the operation of a landfill. The enterprise is a public consortium, licensed by the responsible environmental agency, and is located in the northwest region of the State of Rio Grande do Sul, in the Volcanic Plateau Province of Serra Geral. Thus, there were performed studies of the soil, involving physical, chemical and geotechnical parameters. Regarding the groundwater quality parameters, there were evaluated the water of four active monitoring wells and one of supply, besides the water level variation in a period exceeding hydrologic year. The soil was classified as very clayey, with average clay content of 86 %, and predominance of micropores, common in clayey soils. The saturated hydraulic conductivity of the not compacted soil presented values in the order of 10-4 cm.s-1. Geotechnical parameters were within the described by current standards, with mean values of liquid limit, plastic and shrinkage of 68,83, 41,73 and 28,94 %, respectively, being the soil classified like highly plastic. In relation to the clay fraction, its colloidal activity was classified with low activity, with the presence of non-expansive kaolinite 1:1. The soil presented low values of cation exchange capacity, it was also identified that only copper and chrome elements were above proposed by State law. In relation to the qualitative parameters of groundwater, was identified changes in the concentration of coliforms, nitrate and ammoniacal nitrogen, in some of the samples. In the quantitative matter the area showed a wide variation in water levels, and the rainfall showed significant correlation at 5 % with the water level in three monitoring wells (01, 03 and 05), situated in different positions in the landscape. Regarding the aquifer vulnerability to contamination, the area was classified as a low vulnerability area. Thus, it is concluded that the shallow aquifer in the study area showed variable behavior, in local and regional scales. Changes were identified in the quality of the groundwater in some samples in different periods, between 2007 and 2015.
A questão envolvendo a gestão adequada dos resíduos sólidos urbanos é um grave problema que afeta principalmente os países em desenvolvimento, assim como o Brasil. Apenas no ano de 2010, com a implementação da Política Nacional dos Resíduos Sólidos, a partir da Lei Federal Nº 12.305, essa questão começou a ganhar espaço no meio social e econômico. Nessa lei, uma entre as propostas apresentadas, é a eliminação e recuperação dos locais inapropriados para a disposição dos resíduos urbanos. As consequências adversas da disposição de resíduos envolvem duas questões fundamentais, uma relativa à migração dos contaminantes e outra que trata da estabilidade dos locais usados para sua disposição. Nesse sentido, este estudo tem por objetivo analisar o suporte do meio geológico para a operação de um aterro sanitário. O empreendimento é um consórcio público, licenciado pelo órgão ambiental competente, e está localizado na região noroeste do Estado do Rio Grande do Sul, na Província Vulcânica do Planalto da Serra Geral. Assim, foram realizados estudos de solo, envolvendo parâmetros físicos, químicos e geotécnicos. Em relação à água subterrânea, foram avaliados parâmetros de qualidade da água de quatro poços de monitoramento ativos e um de abastecimento, além da variação do nível da água em um período superior a um ano hidrológico. O solo foi classificado como muito argiloso, com teores de argila médios de 86 %, e predominância de microporos, comuns em solos argilosos. A condutividade hidráulica saturada do solo não compactado apresentou valores na ordem de 10-4 cm.s-1. Os parâmetros geotécnicos estiveram dentro dos descritos pelas normas vigentes, com valores médios de limite de liquidez, plasticidade e contração de 68,83, 41,73 e 28,94 %, respectivamente, sendo o solo classificado como altamente plástico. Em relação a fração argila, sua atividade coloidal foi classificada como de baixa atividade, com presença do argilomineral não expansivo caulinita 1:1. O solo apresentou baixos valores de capacidade de troca de cátions, também foi identificado que apenas os elementos Cobre e Cromo estiveram acima do proposto pela legislação do Estado. No que se refere aos parâmetros qualitativos da água subterrânea, identificou-se alterações na concentração de coliformes termotolerantes, nitrato e nitrogênio amoniacal, em algumas amostras. Na questão quantitativa, a área apresentou uma grande variação no nível da água, sendo que a precipitação pluviométrica indicou correlação significativa ao nível de 5 % com o nível da água em três poços de monitoramento (01, 03 e 05), situadas em distintas posições na paisagem. Em relação à vulnerabilidade do aquífero à contaminação, a área foi classificada como de baixa vulnerabilidade. Com isso, conclui-se que o aquífero raso na área do estudo apresentou comportamento variável, em escala local e regional. Foram identificadas alterações na qualidade da água subterrânea em algumas amostras em distintos períodos, entre os anos de 2007 e 2015.

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2017-10-27T12:25:12Z No. of bitstreams: 0
Made available in DSpace on 2017-10-27T12:25:12Z (GMT). No. of bitstreams: 0
Nas ultimas décadas o processo de biossorção tem alcançado grande relevância no tratamento de efluentes contendo metais potencialmente tóxicos. O uso de bactérias nesse processo tem obtido destaque, uma vez que possuem inúmeras vantagens. O presente estudo pretendeu avaliar o mecanismo envolvido no processo de biossorção dos íons Pb(II) e Hg(II) por meio das linhagens Cupriavidus metallidurans (CH34) e Cupriavidus metallidurans (CH34/pCM3). Dentre os modelos estudados a isoterma de Langmuir foi a que melhor se ajusta ao processo de adsorção, apresentando uma capacidade máxima de adsorção (qmax) de 0,98 mg.g-1 para o Hg(II) e 86,2 mg.g-1 para o Pb(II), para a linhagem selvagem. Já para a linhagem recombinante o qmax obtido foi 3,4 mg.g-1 para o mercúrio e 172,4mg g-1 para o chumbo. Baseado nos valores referentes à energia livre de Gibbs (ΔG) o processo de retenção ocorreu de forma química e espontânea. A influencia do pH foi avaliada por meio de estudo competitivo entre os íons metálicos, em níveis equimolares. O valor que melhor contemplou a adsorção para ambos os íons foi o pH 7,0, tendo o Pb(II) demonstrado maior capacidade de retenção. Em pH 2,0 houve maior retenção do Hg (II), já em pH 10,0 o Pb(II) obteve maior retenção. Indicando que o meio influencia diretamente na competição dos íons metálicos pelos sítios ativos. Constatou-se que a retenção do metal é robusta e estável ao longo de 6 meses. Os resultados indicam que a Cupriavidus metallidurans (CH34/pCM3) pode ser uma boa opção para biossorção de íons metálicos por meio de biorreator.
Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Submitted by Marco Antonio Oliveira da Silva (maosilva@ipen.br) on 2017-05-25T13:07:01Z No. of bitstreams: 0
Made available in DSpace on 2017-05-25T13:07:01Z (GMT). No. of bitstreams: 0
Durante a exploração de uma mina, vários impactos são causados no meio ambiente, entre eles a geração da drenagem ácida de minas (DAM), que consiste da exposição de minerais sulfetados ao ar, água e microorganismos do tipo ferroxidantes, apresentando reações de oxidação e formação de ácido sulfúrico solubilizando metais ali presentes contaminando o solo e as águas. O objetivo deste trabalho de pesquisa foi estudar uma solução tecnológica fazendo uso da oxidação avançada com ozônio de metais pesados presentes em efluentes contaminados, em mina de urânio, com especial foco na remoção do manganês. A mina de urânio das Indústrias Nucleares do Brasil INB, em Caldas, Minas Gerais, local de aplicação deste estudo, enfrenta o problema da DAM e tem como principais contaminantes de suas águas superficiais os elementos, alumínio (Al), manganês (Mn), zinco (Zn), ferro (Fe), sulfatos (SO4+2), fluoretos (F-), metais de terras raras, alem do urânio (U) e do tório (Th). Os testes com ozônio realizados em laboratório com os efluentes da INB e in situ, mostraram uma grande eficiência para remoção do ferro, manganês e cério em até 99%. A concentração total de manganês ficou abaixo dos limites estabelecidos pela resolução 430 e 357 do CONAMA. Elementos como neodímio (Nd), lantânio (La) e zinco (Zn) pouco se oxidam com O3. O Al se mantém praticamente inalterado, enquanto que o tório e o urânio decaem, mas com o passar do tempo de ozonização voltam a se concentrar, porém com um valor inferior ao inicial. O precipitado obtido após a ozonização consiste de até 85% de oxido de manganês. A fim de descartar, após a ozonização, o efluente líquido para o ambiente é necessário uma correção do pH, de modo a atender os parâmetros da legislação CONAMA, sendo utilizado 50 a 86% menos reagente (CaOH2), do que as quantidades utilizadas no processo adotado pela INB.
Dissertação (Mestrado em Tecnologia Nuclear)
IPEN/D
Instituto de Pesquisas Energéticas e Nucleares - IPEN-CNEN/SP

Le développement industriel et urbain accroit la pollution des eaux au Cameroun. Il faut donc rechercher des méthodes de dépollution peu onéreuses et de mise en oeuvre facile. L'objectif de ce travail était d'éliminer les métaux lourds (Cu2+, Pb2+, Hg2+, Cr3+) des eaux usées, par adsorption sur de l'argile brute ou traité thermiquement. L'argile alluviale prélevée dans la région de l'Extrême Nord du Cameroun est essentiellement composée de smectite (46%), kaolinite (38%), interstratifiés (10%) et quartz (5%). Les formules structurales sont (Si3,42Al0,58)(Al0,87Fe0,96Mg0,17)O10(OH)2(C+)0,75 , pour la smectite et Si2Al1,95Fe0,05O5(OH)4. pour la kaolinite. Les cations de métaux lourds s'adsorbent très rapidement sur l'argile brute ; la température et le pH de la solution influencent peu leur adsorption. L'affinité de l'argile pour Cu2+, et Pb2+ est très forte mais faible pour Hg2+ et Cr3+. Le mécanisme proposé est l'échange cationique et la complexation de surface pour l'adsorption de Cu2+, Pb2+ et Cr3+ et un mécanisme de spéciation pour l'adsorption de Hg2+. Les boulettes obtenues par traitement thermique de l'argile au dessus de 500°C sont stables en solution et montrent une bonne capacité d'adsorption des métaux lourds. Les boulettes sont moins efficaces que l'argile brute, mais leur utilisation, évitant la séparation solide-liquide, après adsorption est plus facile
The industrial and urban development increases the water pollution in Cameroon. It becomes imperative to develop inexpensive and easy to manage remediation methods. This work aimed at eliminating heavy metals (Cu2+, Pb2+, Hg2+, Cr3+) from water by adsorption on raw or heat treated clay. The alluvial clay sampled in the far North of Cameroon mainly contains smectite (46%), kaolinite (38%), interlayers (10%) and quartz (5%). The structural formulas are : (Si3,42Al0,58)(Al0,87Fe0,96Mg0,17)O10(OH)2(C+)0,75 for the smectite and Si2Al1,95Fe0,05O5(OH)4 for the kaolinite. The heavy metals cations fastly adsorb on raw clay, the temperature and the pH have not much influence on their adsorption. The clay affinity in relation to Cu2+, and Pb2+ is very strong whereas it is low for Hg2+, Cr3+. For the adsorption of Cu2+, Pb2+ and Cr3+ the proposed mechanisms are the cation exchange and the complexation while for the Hg2+, a mechanism of speciation is involved. The pellets obtained by thremic treatment of the clay above 500°C are stable in solution and they have a good capacity for heavy metals adsorption. Performances of the pellets are lower than those of raw clay, however, their use is easier since they do not need solid-liquid separation after adsorption

Submitted by Emanuel Varela Cardoso (emanuel.varela@ufcg.edu.br) on 2018-09-28T19:41:20Z No. of bitstreams: 1 JOELMA MORAIS FERREIRA – TESE (PPGEP) 2006.pdf: 9831105 bytes, checksum: 2ef86ebc8b2b5d26c22e23ceaa696d0d (MD5)
Made available in DSpace on 2018-09-28T19:41:20Z (GMT). No. of bitstreams: 1 JOELMA MORAIS FERREIRA – TESE (PPGEP) 2006.pdf: 9831105 bytes, checksum: 2ef86ebc8b2b5d26c22e23ceaa696d0d (MD5) Previous issue date: 2006-12-22
CNPq
As atividades industriais têm introduzido metais nas águas numa quantidade muito maior do que aquela que seria natural, causando grandes poluições. Os tratamentos convencionais (redução química, troca iônica, ultrafiltração e osmose inversa), normalmente usados para a remoção de metais dos efluentes líquidos, apresentam algumas desvantagens, pois além de serem, na maioria, processos caros, não conseguem remover totalmente os íons metálicos. A necessidade de tratamentos eficientes e econômicos para remoção de íons metálicos de efluentes tem resultado no desenvolvimento de novas tecnologias. Muitas destas descrevem técnicas envolvendo o uso de bactérias, fungos, microalgas, e macroalgas. A biossorção é o processo no qual sólidos de origem biológica ou seus derivados são usados na retenção de íons metálicos de um ambiente aquoso. Comparadas às metodologias convencionais para a remoção de íons metálicos de efluentes industriais, o processo de biossorção tem como principais vantagens o baixo custo operacional e alta seletividade. Dentre os microrganismos mais utilizados destacam-se os fungos, que são utilizados em uma variedade de processos industriais servindo como fonte constante e econômica de suprimento de biomassa para remoção de íons metálicos. Sendo o Brasil, o maior produtor mundial de álcool etílico via processo fermentativo utilizando-se da Saccharomyces cerevisiae (levedura) como o microrganismo agente da fermentação, é prática comum nas indústrias de produção de álcool etílico, no Brasil, a sangria do creme de levedura, que consiste em retirar parte do creme do processo de centrifugação. Desta forma, a Saccharomyces cerevisiae é uma fonte excedente do processo de fermentação que pode ser utilizada, por exemplo, como bioadsorvente de íons metálicos em processos de descontaminação ambiental. Experimentos de biossorção de íons metálicos utilizando a Saccharomyces cerevisiae para remoção do Cd2+ e Pb2+ foram realizados para investigar os fatores que influenciam e otimizam o processo de biossorção. Através do estudo da cinética estático verificou-se que o tempo 48h já é suficiente para o processo alcançar o equilíbrio. Para a cinética dinâmica a partir de 90 min não ocorreu mais alteração no valor da concentração final dos dois íons metálicos, portanto, sendo este tempo suficiente para o sistema alcançar o equilíbrio num sistema operando em condições dinâmicas. A técnica de planejamento experimental foi utilizada para avaliar os efeitos das variáveis quantidade de biomassa, concentração dos íons metálicos, temperatura, pH e estado da biomassa (viva ou morta), que influenciam no processo Os efeitos da quantidade de biomassa e concentração inicial dos íons metálicos estudados foram as variáveis que apresentaram mais efeitos significativos quando comparado com o efeito do pH, estado da biomassa (viva ou morta) e temperatura nas condições avaliadas. O modelo que melhor ajustou o processo foi o de Langmuir com valores de qmax de 210,5 mg.g-1 para o cádmio e 1486,88 mg.g-1 para o chumbo. A levedura imobilizada apresentou uma certa queda na sua eficiência de remoção observando-se redução média na eficiência de q de 78,5% para o Cd2+ e de 73,92% para o Pb2+.
The industrial activities have introduced metals in waters in quantities which are greater than those found naturally, thereby causing heavy pollutions. The conventional treatments (chemical reduction, ionic exchange, ultrafiltration and inverse osmosis), normally used for the metal removal of the liquid effluents, present some disadvantages, because majority of them apart from being expensive processes are not capable to remove metal ions compleatly. The necessity of efficient and economic treatments for removal of metallic ions from effluents has resulted in the development of new technologies. Many of these techniques are based on the use of bacteria, fungi, microseaweed, and macroseaweed. The biosorption is a process in which solids of natural origin or its derivatives are used in the retention of metallic ions from an aqueous medium. The biosorption process has as main advantages the low operational cost and high selectivity when compared to the conventional methods for the removal of metallic ions from industrial effluents. Amongst the used microorganisms fungi are more distinguished, as these are used in a variety of industrial processes and serves as constant and economic source of supplement of biomass for removal of metallic ions. Brazil being a world-wide big producer of ethyl alcohol by a fermentative process that uses the Saccharomyces cerevisiae (ferment) as the microorganism, it is a common practice in the industries of alcohol to remove the excess of the ferment cream by centrifuging. This way, the excessive Saccharomyces cerevisiae of the fermentation process is a source that can be used, for example, as biosorbent of metallic íons for the decontamination of environment. Experiments of biosorption of metallic íons using the Saccharomyces cerevisiae for removal of the Cd2+ and Pb2+ had been carried out to investigate the factors that influence and optimize the biosorption process. Through the study of the static kinetics it was verified that a period of 48 hours is enough for the process to reach the equilibrium. For the dynamic kinetics after 90 min no more change in the final concentration of the two metallic ions occurred. Therefore, this time is enough for the system to reach the equilibrium when the process is operating in dynamic conditions. The design of experiment technique was used to evaluate the effect of the variables: biomass amount, metallic ions concentrations, temperature, pH and state of the biomass (alive or dead). The effects of the amount of biomass amount and initial metallic ion concentration were the variables that presented more significant effects when compared with the effect of pH and state of the biomass (alive or dead) under the evaluated conditions. The Langmuir and Freundlich models were used to adjust to the experimental data of the adsorption isotherms of metal ions studied. The model that adjusted better the adsorption isotherms was of Langmuir having qmax values as 210.5 mg.g-1 for cadmium and 1486.88 mg.g-1 (Langmuir not linearized) for the lead. The immobilized ferment presented a decrease in its efficiency of metal ion removal. In the study for the immobilized ferment an average efficiency of the adsorbed amount per unit of mass of 78.5% for the Cd2+ and 73.92% for the Pb2+ was observed.

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química Pela Universidade Nova de Lisboa,Faculdade de Ciências e Tecn
The main objective of this research was the recovery of natural carbon- containing wastes into environmentally friendly secondary products, and their re-use as selective adsorbents for heavy metals removal from wastewater streams. The natural carbon containing wastes were: Sunflower husks, D-grade coal, AKKhZ sludge and Spent petroleum product waste. To achieve this purpose, the research was focused on three different types of studies: 1. Study the thermolysis process of the single carbon-containing wastes components and their blends aimed at: (i) determination of the reference onset of the thermal stages, assigning the reference structural fragments of the parent Sunflower husks, D-grade coal, AKKhZ sludge and Spent petroleum product waste; and (ii) evaluation of the synergetic effects observed during their co-thermolysis. 2. Development of a recovery concept to the waste recycling via co-activation of the co-mingled carbon-containing waste materials, in order to obtain a porous activated carbon. 3. Optimization of the experimental conditions for the adsorption of heavy metals from contaminated waste waters. In order to gain some insight into the reactions which may occur between the components of the co-mingled wastes during the activation process, in the first part of the work the pyrolysis behavior of the single components and their blends were investigated by thermogravimetric analysis. On this stage, the data obtained suggested a new approach to the problem of assessing the selectivity of the co-processing concept. Based on the direct monitoring of the reference structural fragments during co-thermolysis, the synergetic effects were evaluated for the co-mingled systems. The data obtained were used in the second part of the work, for the development of the co-activation concept to the co-mingled solid and liquid recovery into secondary solid porous products. The development of the design parameters for the activated carbons syntheses was done considering the re-polymerization, re- association and the polycondensation reactions between the reference structural fragments of the components in the ternary composite systems «Spent Petroleum Product Waste – Biomass – D-grade D» and «AKKhZ sludge – Biomass – D-grade coal». The factors influencing the char formation and the properties of the resulting activated carbons were evaluated at laboratory scale. The co- activation approach developed to the solid and liquid co-mingled waste recycling, was implemented at pilot scale. Novel powder and granular activated carbons have been obtained with surface area of 400-1050 m2/g, total pore volume of 0.32-0.47 m3/g and yield of 21-27%.A comprehensive adsorption study using the novel activated carbons, was performed in the third part of the work. The influence of various textural and surface characteristics of carbon materials (porosity, surface area, oxygen functional groups) and the conditions of the adsorption process (initial solution acidity, contact time, components ratio) were investigated in batch mode for single- and multi-component model solutions containing Fe (II), Co (II), Cu (II), Cr (III), Ni (II), Mn (II). Under optimized conditions, a total chromium uptake of 1.09 mmol/g was achieved using as adsorbent the novel activated carbon from co-mingled wastes. The uptake is slightly higher than the one obtained for the commercial GAC Norit 1240 Plus (A– 10128) activated carbon oxidised by HNO3. Moreover, in the course of this work, it became clear, that the usage of the activated carbon from co-mingled waste for the 3d transitional metals adsorption offered an attractive approach to simultaneous metal removal from multi-component solutions. The total metal removal combined the process of metal hydroxide precipitation (up to 50–55 % by total removal) with the metal cation adsorption on negatively charged carbon surface (up to 15–20 % by total removal) in a single operation unit. Finally, the mechanism of the 3d transition metals adsorption on the activated carbon from co-mingled waste was considered. Within this context, the natural organic waste recovery into porous solid environmentally friendly products offered a technological alternative

M. Tech. (Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology|
The co-existence of organic acids and toxic heavy metals in natural water creates harmful effects on human, plants and animals. Therefore, it is necessary to treat organic acids and toxic heavy metal contaminated wastewater prior to its discharge to the environment. The aim of this study was to apply co-treatment of industrial wastewater containing citric acid and toxic heavy metals in single and binary systems using photocatalysis process. The hydrothermal method was used to synthesise dandelion-like TiO2 structures. Modifications of the dandelion-like TiO2 by deposition of gold nanoparticles and immobilisation on calcium alginate were done using deposition precipitation and one-step encapsulation methods, respectively. Dandelion-like TiO2 and dandelion-like TiO2 immobilised on calcium alginate (Alg/TiO2) were used as photocatalysts for Cr(VI), Hg(II) and citric acid removal from water. The results showed that the production of dandelion-like TiO2 structures strongly depends on the reaction time and synthesis temperature as key process parameters. The characterisation of the dandelion-like TiO2 by X-ray diffraction (XRD), transmission electron microscope (TEM), scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and Brunauer-Emmett-Teller (BET) revealed the crystal structure, morphology, chemical composition and surface area. It was found that the efficiency of photocatalytic process depends on the type of pollutants, initial pH of the solution, photocatalyst dosage, contact time, substrate initial concentration, UV wavelength and light intensity. The reduction efficiency of Cr(VI) ion and citric acid increased with decreasing the initial pH values and initial concentration. On the other hand, Hg(II) reduction efficiency increased with increasing the initial pH values and initial concentration. In a binary system, the reduction of Cr(VI) and Hg(II) was found to be faster than in the single and ternary systems. The relationship of the chemical reaction rate of Cr(VI), Hg(II) and citric acid were expressed by the pseudo-first-order kinetic equation. Addition of ferric ions to Cr(VI)-citric acid complex and Hg(II)-citric acid complex enhanced the reduction of Cr(VI) and Hg(II), a complete reduction was accomplished within 30 and 60 minutes (min) of irradiation time, respectively. The reduction efficiency of both Cr(VI) and Hg(II) in the presence of citric acid in a solution was still significant after four times of Alg/TiO2 reuse. These results indicated that the UV/TiO2 photocatalysis process can be considered as a suitable method to reach a complete reduction of Cr(VI) and Hg(II) in the presence of citric acid in a solution.

M. Tech. Chemical Engineering
Environmental pollution due to heavy metals is a global crisis. Contamination as a result of heavy metals from industries such as mining operations, electroplating facilities, etc. pose serious threats to the aquatic ecosystem, people and the environment. Lead (Pb), cadmium (Cd), zinc (Zn), copper (Cu), mercury (Hg) and nickel (Ni) are common examples of heavy metal ions often detected in most effluents. They are characterised by their non-biodegradability, toxicity and tendency to accumulate in living organisms, and thereafter, cause various diseases and disorders. In this study, two nano-structured composite bio-sorbents were prepared to determine their metal binding capacity, effect of solution pH, contact time and elution in a magnetically assisted adsorption system. Consequently, this study aims to develop magnetically assisted adsorption process for industrial wastewater treatment for re-use.

碩士
國立宜蘭大學
環境工程學系碩士班
105
In recent years, it is important to pay more attention for heavy metal removal due to increasing environmental awareness. In Taiwan, the sewage treatment plant produces about 4 million tons/year sludge (80% moisture) and nearly 60% of the sludge is not adequately treated. The main traditional treatment of sludge is direct burial. However, direct burial not only occupies the land, but also increases the possibility of groundwater pollution. The residue still needs to be further processed since it contains heavy metal, although some methods such as drying and burning can stabilize the nature of the sludge and reduce its volume. At present, the traditional heavy metal wastewater treatment is adsorption. The activated carbon is used very often because the activated carbon has a very high specific surface area and internal porous structure. In addition, the presence of functional groups on the surface will enhance the adsorption capacity. Activated carbonization sludge owns high porosity and high specific surface area. Furthermore, the operation cost of carbonated sludge is low since sludge is reused and recycled. Domestic sewage sludge Carbon (DSSC) was prepared in this study to reduce the cost of adsorbent. The DSSC was activated with an activator, such as zinc chloride (ZnCl2). The activated DSSC has porous structure, high specific surface area and uniform pore distribution, and a good adsorption capacity. In this study, activated DSSC was used to adsorb heavy metals in wastewater and compare with AC. The prepared material characteristics were be analyzed with BET, SEM-EDS, FTIR, TGA, ICP-AES, UV-VIS. The results show that the maximum specific surface area is 490 m2 g-1. The isothermal adsorption/desorption curves belong to type Ⅳ curve with N2 isothermal adsorption/desorption instrument. The adsorption capacity of DSSC is 15.1, 28.9, 48.3 and 68.8mg g-1, respectively, when the Cr(VI) concentration of wastewater is 15, 30, 60 and 120 ppm. In contrast, the adsorption capacity of AC is only 0.04, 0.07, 0.12 and 0.17 mg g-1, respectively. The best ratio of DSSC and ZnCl2 was 1: 1, and the maximum adsorption capacity was 68.8 mg g-1. This study also aimed at effects of operation parameters, such as Cr(VI) concentration, pH, dosage and temperature, on Cr(VI) removal performance. The results also show the Cr (VI) removal efficiency was about 90% at a lower pH value (pH = 1.5-2), adsorption dose 1g L-1 under 35oC. In other hand, the mathematical models, such as adsorption kinetics model, isothermal adsorption mode, thermodynamic model and particle diffusion mode, were also obtained by means of model analysis for predicting the possible impact of the reaction.

碩士
國立宜蘭大學
環境工程學系碩士班
104
Soil contamination is an urgent problem which should be solved instantly. Chemical stabilization technique has been used for reclamation of contaminated soils due to several advantages, including easy operation, inexpensive, and friendly for environment. This method has been employed to substitute other expensive techniques for recovery of the industrial areas and farmlands. The objective of this study is using aquaculture’s wastes, including coral bone, natural zeolite, and activated carbon, as chemical stabilizers for treatment of three farmland soils which contaminated with Cu, Zn, Ni, Cd, and Pb. The variations in Cu, Zn, Ni, Cd, and Pb extractabilities and major nutrients in soil were examined when the stabilization reagents were added through an experiment performed with simulating natural precipitation. The results showed that the stabilization reagent with the smallest size could cause the highest decrease in metallic extractability. Furthermore, stabilization reagent which suppressed the extractability of heavy metal was followed the order: coral bone > activated carbon > zeolite. Sample A (a soil contaminated with Cu, Zn, and Ni): After treatment with both used zeolite and fresh zeolite, the Cu, Zn, Ni extractabilities declined to about 57, 74, 58, 43, 65, and 58% of their original levels respectively. The Cu, Zn, Ni extractabilities declined to about 43, 48, 42, 43, 43, and 25% of their original levels after the additions of used carol bone and fresh carol bone respectively. The Cu, Zn, Ni extractabilities declined to about 43, 70, 50, 29, 57, and 23% of their original levels after the additions of used activated carbon and and fresh activated carbon respectively. After the addition of zeolite nitrogen extractability level became 1.1 and 1.4 times higher than that obtained by additions of used carol bone and used activated carbon. Extractable phosphorus content in soil increased 2.3 times its original level after the addition of used zeolite, however, this level declined to only 14% and 57% of initial level when the soil was treated with used carol bone and used activated carbon, respectively. Extractable potassium content obtained by used carol bone treatment was 1.7 and 1.8 times higher than those treated by used zeolite and used activated carbon treatments. Sample B (a soil only contaminated with Cd): Stabilization reagent suppressed the Cd extractability was followed the order: coral bone > activated carbon > zeolite. The Cd extractability declined to about 40, 50, 20, 30, 30, and 50% of their original levels after the additions of used zeolite, fresh zeolite, used carol bone, fresh carol bone, used activated carbon, and fresh activated carbon, respectively. After the addition of carol bone, nitrogen extractability level in soil became 1.3 and 1.2 times higher than that obtained by treatment with used zeolite and used activated carbon. Extractable phosphorus content in soil increased 1.2 times its original level after the addition of used zeolite, however, this level declined to only 23% and 77% of initial level when the soil was treated with used carol bone and used activated carbon, respectively. Extractable potassium content in soil obtained by treatment with used carol bone became 1.4 and 1.5 times higher than those treated by used zeolite and used activated carbon. Sample C (a soil only contaminated with Pb): Stabilization reagent which suppressed the Cd extractability was followed the order: coral bone > activated carbon > zeolite. The Pb extractability declined to about 33, 56, 0, 22, 33, and 56% of their original levels after the additions of used zeolite, fresh zeolite, used carol bone, fresh carol bone, used activated carbon, and fresh activated carbon, respectively. After the addition of carol bone, nitrogen extractability level in soil became 1.2 and 1.1 times higher than that obtained by additions of used zeolite and used activated carbon. After the addition of used zeolite, extractable phosphorus content in soil slightly increased, however, this level declined to only 0% and 40% of initial level when the soil was treated with used carol bone and used activated carbon, respectively. The change of extractable potassium content was insignificant by the treatment of all stabilization reagents for all soil samples. Carol bone had high priority in recommendation for the remediation of farmland contaminated with heavy metals. Keywords: heavy metal, extractability, Chemical stabilization, Zeoilite, Activated carbon, Coral bone

碩士
國立中興大學
土壤學系
84
The effect of electroplating waste water to heavy metals accumulated forms in soil system and to agricultural products Chang-Chien, Shui Wen Abstract In recent years the industrialization has been rapidly developed in Taiwan. the heavy metals such as Ni, Zn, Pb, Cu, Cr and Cd are easily penetrated into soil environment by the industrial waste materials. Different forms of heavy metals maintain circulating equilibrium with diffused metal in the soil solution. Therefore, the purpose of this research is to investigateand discuss the effects of electroplating waste water to heavy metals accumulated forms in soil system and to agricultural products. This study was conducted by supplying different quantities of electroplating waste water into planted and unplanted plots of rape greens under irrigation. After harvest, the concentrations of heavy metals contained within the plants and the contents and forms of heavy metals left at the soil were measured to compare the relationships between the former and the latter when supplying different types of water quantities.This was to understand what effect the electroplating waste water could cause on metals accumulated forms in soil system and on agricultural products. The results showed Ni, Zn, Pb, Cu, Cr and Cd contained big portion as residual forms (89%~22%), rarely as exchangeable forms (0%~2.6%) at the soil system. Moreover, due to the different water quality and quantity supplements, even in the same soil system the content of different heavy metals forms differed among exchangeable form, carbonate form, Fe-Mn oxide form and organic form. Also, as the supplement of waste water increased, the four forms mentioned above responded with irregular formulas independently. The results of correlation comparison was analyzed by applying aqua regia, 0.1M HCl, and sequential extraction procedure to extract the content of heavy metals contained within the Chinese mustard and the heavy metals left in the soil. Exchangeable form, carbonate form, Fe- Mn oxide form and organic form from the sequential extraction procedure were abler to respond to the ability of Chinese mustard taking up heavy metals than others. This phenomenon interpreted that the different forms of heavy metal existed in the soil system and its effective content could affect the uptake ability of crops.The concentration of heavy metals in Chinese mustard increased by increasing the quality of electroplating waste water. But, when the amount of heavy metals in the soil and plant was less than the toxicant level, the heaviness of oven-dry matter would not decrease by the increasing amount of heavy metals under irrigation.

Industrial effluents with high concentrations of heavy metals are widespread pollutants of great concerns as they are known to be persistent and non-degradable. Continuous monitoring and treatment of the effluents become pertinent because of their impacts on wastewater treatment plants. The aim of this study is to determine the correlation between heavy metal pollution in water and the location of industries in order to ascertain the effectiveness of the municipal waste water treatment plant. Heavy metal identification and physico-chemical analysis were done using Inductively Coupled Plasma Optical Emission Spectrometry (ICP-OES) and multi-parameter probe respectively. Correlation coefficients of the measured values were done to investigate the effect of the industrial effluents on the treatment plants. Heavy metal resistant bacteria were identified and characterised by polymerase chain reaction and sequencing. Leeuwkuil wastewater treatment plants were effective in maintaining temperature, pH, and chemical oxygen demand within South Africa green drop and SAGG Standards whereas the purification plant was effective in maintaining the values of Cu, Zn, Al, temperature, BOD, COD, and TDS within the SANS and WHO standard for potable water. This findings indicated the need for the treatment plants to be reviewed.The industrial wastewater were identified as a point source of heavy metal pollution that influenced Leeuwkuil wastewater treatment plants and the purification plants in Vaal, Vereenining South Africa. Pseudomonas aeruginosa, Serratia marcescens, Bacillus sp. strain and Bacillus toyonensis that showed 100% similarity were found to be resistant to Al, Cu, Pb and Zn. These identified bacteria can be considered for further study in bioremediation.
Environmental Sciences
M. Sc. (Environmental Science)

Στην παρούσα μεταπτυχιακή εργασία παρουσιάζονται τα αποτελέσματα της διερεύνησης της επίδρασης της ιλύος βιολογικού καθαρισμού Καλαμάτας (Β.Κ.Κ.) στην ανάπτυξη του σπανακιού (Spinacia Oleracea) καθώς και στην απαορρόφηση N, P, K, Ca, Mg, ιχοστοιχείων Fe, Mn, Cu, Zn, βαρέων μετάλλων Pb, Ni, Cd και Cο από τα διάφορα μέρη του φυτού. Επιπλέον, η εργασία αυτή αποτελεί μια μελέτη της επίδρασης της συγκεκριμένης ιλύος και σε ορισμένους δείκτες ποιότητας των μιγμάτων ιλύος-εδάφους, όπως pH, αλατότητα, οργανική ουσία, ολικό ανθρακικό ασβέστιο, αλλά και σε ποσοτικούς δείκτες όπως η περιεκτικότητα σε ολικό άζωτο (Ν%), διαθέσιμο φωσφόρο (Ρ κατά Olsen), ανταλλάξιμα κατιόντα K, Ca, Mg, και συγκέντρωση ολικών, διαθέσιμων και ανταλλάξιμων ιχνοστοιχείων Fe, Mn, Cu, Zn, "βαρέων μετάλλων" Pb, Ni, Cd, Cr, Co. Τα αποτελέσματα προέρχονται μετά από πειραματική μελέτη που έγινε σε φυτά σπανακιού, αναπτυσσόμενα σε υποστρώματα που προέκυψαν από ανάμιξη εδάφους και ιλύος σε διάφορες αναλογίες, σε υπαίθριο προστατευμένο χώρο. Σκοπός της πειραματικής αυτής μελέτης είναι να ελεγχθούν και να αξιολογηθούν οι ιδιότητες που αποκτούν τα υπό εξέταση υποστρώματα από την προσθήκη ιλύος στο έδαφος ταυτόχρονα με την επίδραση στην ανάπτυξη του σπανακιού. Έτσι σε αδρές γραμμές μπορούμε να συμπεράνουμε ότι τα αποτελέσματα και η αξιολόγησή τους κατατείνουν στο ότι η ιλύς της μονάδας βιολογικού καθαρισμού της Καλαμάτας μπορεί να αξιοποιηθεί ως λίπασμα σε μικρές αναλογίες ιλύος/εδάφους και φαίνεται ότι η διάθεσή της στο έδαφος για γεωργικούς σκοπούς αποτελεί μια πολύ καλή μέθοδο διάθεσης, που πρέπει να εξετάζεται κατά προτεραιότητα. Ταυτόχρονα, επιβάλλεται η συνέχιση και επέκταση της σχετικής έρευνας, για αξιοποίηση και οικολογική διαχείριση της εν λόγω ιλύος.
This study investigates the effects of the sewage sludge of Kalamata Waste Water Treatment Plant (WWTP) both in the development of spinach (Spinacia oleracea) and the absorption of N, P, K, Ca, Mg, Fe, Mn, Cu, Zn, Pb, Ni, Cd and Co from various spinach plant parts. Parameters of soil - sludge mixtures are also considered during this study. Especially the effect of sludge on parameters such as pH, salinity, organic matter, total CaCO3, total nitrogen content (N%), available phosphorus, exchangeable K, Ca, Mg, and concentration of total, available and exchangeable Fe, Mn, Cu, Zn, Pb, Ni, Cd, Cr, Co. The experiments where conducted in Messinia and the results showed that sludge improves soil fertility. The application of sludge does not cause environmental problems in small proportions of sludge – soil mixture. In large quantities the addition of sludge is associated with potential toxicities and increased salinity in the soil as well as potential environmental problems from over-concentration of phosphorus but also heavy metals such as Pb, Ni and Cr. Special attention is need for Cd, not because of high concentration, but because of the special mobility it presents. Finally this study confirms the presence of a large number of interactions between nutrients, heavy metals and soil properties in soil and spinach. The evaluation of these interactions are of great importance because they help us to quantify elemental contribution of soil and plants, helps in understanding the problems of nutrition in preventing the occurrence of toxic problems at the expense of consumer health, the environment and ultimately to effective use of sludge. Finally, the sludge of Kalamata WWTP can be used as fertilizer in small proportions of sludge / soil mixtures and it seems that the disposal of sludge in soils for agricultural purposes is a very good method of disposal that must be considered.