Removal of Pb(II) ions and malachite green dye from wastewater by activated carbon produced from lemon peel

In the present study, a high-surface area activated carbon was prepared by chemical activation of lemon peel with H3PO4 as the active agent. Then, the adsorption behavior of Malachite green dye and Pb(II) ions on the produced activated carbon was studied. Batch process was employed for sorption kinetics and equilibrium studies. Experimental data were fitted to various isotherm models. According to the Langmuir model, the maximum adsorption capacities of Malachite green dye and Pb(II) ions were found to be 66.67 and 90.91 mg g-1, respectively, at room temperature. Kinetic studies showed the adsorption process followed a pseudo second-order rate model. The sorption kinetics were controlled by intra-particle diffusion. The results indicated that the produced activated carbon can be economically and effectively used as an adsorbent for the removal of Malachite green dye and Pb(II) ions from wastewaters.

Natural and synthetic fibres improving tensile strength and elongation of paper products

The theory part of the Master’s thesis introduces fibres with high tensile strength and elongation used in the production of paper or board. Strong speciality papers are made of bleached softwood long fibre pulp. The aim of the thesis is to find new fibres suitable for paper making to increase either tensile strength, elongation or both properties. The study introduces how fibres bond and what kind of fibres give the strongest bonds into fibre matrix. The fibres that are used the in manufacturing of non-wovens are long and elastic. They are longer than softwood cellulose fibres. The end applications of non-wovens and speciality papers are often the same, for instance, wet napkins or filter media. The study finds out which fibres are used in non-wovens and whether the same fibres could be added to cellulose pulp as armature fibres, what it would require for these fibres to be blended in cellulose, how they would bind with cellulose and whether some binding agents or thermal bonding, such as hot calendaring would be necessary. The following fibres are presented: viscose, polyester, nylon, polyethylene, polypropylene and bicomponent fibres. In the empiric part of the study the most suitable new fibres are selected for making hand sheets in laboratory. Test fibres are blended with long fibre cellulose. The test fibres are viscose (Tencel), polypropylene and polyethylene. Based on the technical values measured in the sheets, the study proposes how to continue trials on paper machine with viscose, polyester, bicomponent and polypropylene fibres.

Lanthanum based high surface area perovskite-type oxide and application in CO and propane combustion

The perovskite-type oxides using transition metals present a promising potential as catalysts in total oxidation reaction. The present work investigates the effect of synthesis by oxidant co-precipitation on the catalytic activity of perovskite-type oxides LaBO3 (B= Co, Ni, Mn) in total oxidation of propane and CO. The perovskite-type oxides were characterized by means of X-ray diffraction, nitrogen adsorption (BET method), thermo gravimetric and differential thermal analysis (ATG-DTA) and X-ray photoelectron spectroscopy (XPS). Through a method involving the oxidant co-precipitation it's possible to obtain catalysts with different BET surface areas, of 33-44 m²/g, according the salts of metal used. The characterization results proved that catalysts have a perovskite phase as well as lanthanum oxide, except LaMnO3, that presents a cationic vacancies and generation for known oxygen excess. The results of catalytic test showed that all oxides have a specific catalytic activity for total oxidation of CO and propane even though the temperatures for total conversion change for each transition metal and substance to be oxidized.

Determination of Alkalinity and dissociation constants of high salinity waters: use of F5BC titration function

Measurements of parameters expressed in terms of carbonic species such as Alkalinity and Acidity of saline waters do not analyze the influence of external parameters to the titration such as Total free and associated Carbonic Species Concentration, activity coefficient, ion pairing formation and Residual Liquid Junction Potential in pH measurements. This paper shows the development of F5BC titration function based on the titrations developed by Gran (1952) for the carbonate system of natural waters. For practical use, samples of saline waters from Pocinhos reservoir in Paraiba were submitted to titration and linear regression analysis. Results showed that F5BC involves F1x and F2x Gran functions determination, respectively, for Alkalinity and Acidity calculations without knowing "a priori" the endpoint of the titration. F5BC also allows the determination of the First and Second Apparent Dissociation Constant of the carbonate system of saline and high ionic strength waters.

Adsorptive removal of harmful organic compound from aqueous solutions

Adsorption is one of the most commonly used methods in water treatment processes. It is attractive due to it easy operation and the availability of a wide variety of commercial adsorbents. This doctoral thesis focuses on investigating and explaining the influence of external phase conditions (temperature, pH, ionic strength, acidity, presence of cosolutes) on adsorption phenomena. In order to cover a wide range of factors and phenomena, case studies were chosen from various fields where adsorption is applied. These include the adsorptive removal of surface active agents (used in cleaning chemicals, for example) from aqueous effluents, the removal of hormones (estradiol) from drinking water, and the adsorption of antibiotics onto silica. The latter can beused to predict the diffusion of antibiotics in the aquatic system if they are released into the environment. Also the adsorption of living cells on functionalized polymers to purify infected water streams was studied. In addition to these examples, the adsorptive separation of harmful compounds from internal water streams within a chemical process was investigated. The model system was removal of fermentation inhibitors from lignocelluloses hydrolyzates. The detoxification of the fermentation broth is an important step in the manufacture of bioethanol from wood, but has not been studied previously in connection with concentrated acid hydrolyzates. New knowledge on adsorption phenomena was generated for all of the applications investigated. In most cases, the results could be explained by combining classical theories for individual phenomena. As an example, it was demonstrated how liquid phase aggregation could explain abnormal-looking adsorption equilibrium data. In addition to the fundamental phenomena, also process performance was of interest. This aspect is often neglected in adsorption studies. It was demonstrated that adsorbents should not be selected for a target application based on their adsorption properties only, but regeneration of the spent adsorbent must be considered. It was found that using a suitable amount of organic co-solvent in the regeneration can significantly improve the productivity of the process.

Physiological cost of induced resistance in cotton plants at different nitrogen levels

Resistance induction through the use of chemical inducers often results in physiological costs to the plant. In this study, induced resistance in cotton plants was evaluated with regard to physiological costs in a cultivar susceptible to Colletotrichum gossypii var. cephalosporioides (CNPA GO 2002 - 7997). Plants were cultivated in substrates with two levels of nitrogen and received two applications of acibenzolar-S-methyl (ASM), jasmonic acid (JA) and Agro-Mos® (AM) disease resistance inducers. Plant height (H), internodal length (IL), shoot fresh weight (SFW), root fresh weight (RFW), shoot dry weight (SDW) and root dry weight (RDW) were evaluated. The activity of the phenylalanine ammonia lyase (PAL) and peroxidase (POX) was also determined. The plants treated with ASM presented high physiological costs with an accentuated reduction in H, SFW and SDW, whereas those treated with JA exhibited a significant increase in SDW, and did not significantly differ from H and IL. In the potting mix supplemented with nitrogen, all inducers differed from the control treatment regarding to internodal length, whereas only ASM and AM presented a significant difference between one another in the potting mix without the addition of nitrogen. Significant correlations (P=0.05) were found for most of the variables analyzed, with greater correlations observed between SFW and SDW (0.94); IL and H (0.74); SFW and H (0.70); and SDW and H (0.70). ASM induced the least amount of PAL activity, significantly differing from the remaining treatments. Greater POX activity was observed in ASM, which significantly differed from the control. AM and JA, however, presented lower activity than the control with regard to these enzymes, and it was not possible to confirm induction resistance in these two treatments.

EDTA- and DTPA-functionalized silica gel and chitosan adsorbents for the removal of heavy metals from aqueous solutions

Adsorbents functionalized with chelating agents are effective in removal of heavy metals from aqueous solutions. Important properties of such adsorbents are high binding affinity as well as regenerability. In this study, aminopolycarboxylic acid, EDTA and DTPA, were immobilized on the surface of silica gel, chitosan, and their hybrid materials to achieve chelating adsorbents for heavy metals such as Co(II), Ni(II), Cd(II), and Pb(II). New knowledge about the adsorption properties of EDTA- and DTPA-functionalizedadsorbents was obtained. Experimental work showed the effectiveness, regenerability, and stability of the studied adsorbents. Both advantages and disadvantages of the adsorbents were evaluated. For example, the EDTA-functionalized chitosan-silica hybrid materials combined the benefits of the silica gel and chitosan while at the same time diminishing their observed drawbacks. Modeling of adsorption kinetics and isotherms is an important step in design process. Therefore, several kinetic and isotherm models were introduced and applied in this work. Important aspects such as effect of error function, data range, initial guess values, and linearization were discussed and investigated. The selection of the most suitable model was conducted by comparing the experimental and simulated data as well as evaluating the correspondence between the theory behind the model and properties of the adsorbent. In addition, modeling of two-component data was conducted using various extended isotherms. Modeling results for both one- and twocomponent systems supported each other. Finally, application testing of EDTA- and DTPA-functionalized adsorbents was conducted. The most important result was the applicability of DTPA-functionalized silica gel and chitosan in the capturing of Co(II) from its aqueous EDTA-chelate. Moreover, these adsorbents were efficient in various solution matrices. In addition, separation of Ni(II) from Co(II) and Ni(II) and Pb(II) from Co(II) and Cd(II) was observed in two- and multimetal systems. Lastly, prior to their analysis, EDTA- and DTPA-functionalized silica gels were successfully used to preconcentrate metal ions from both pure and salty waters

Improvement of Surface Strength of Paper

Offset printing is a popular printing method that is especially suitable for large and fast print jobs. Newspapers, magazines and books are typical examples of products printed with offset method. In high volume printing production high efficiency is essential. Offset printing uses tacky inks that cause serious stress to the paper surface. Dusting and linting are terms that describe how loose and weakly bonded particles are removed from the paper surface in the printing process. The removed particles accumulate in the process causing deteriorating print quality. This forces the printing operators to stop production for washing and cleaning. Time and money are lost. Dusting and linting tendency of paper can be decreased by improving the surface strength of paper. In the present work a method to increase the surface strength of paper was studied. In the literature part offset printing method and challenges related to offset printing are presented. A review of new methods for surface sizing of paper is also presented. The experimental part presents trials where an apparatus for improving paper surface strength was tested and developed in mill scale. Laboratory work supporting the actual mill scale operations is also presented. The acquired results provide a solid base of information to make decisions on how to proceed with research in the present field of study.

Sewage Sludge Electro-Dewatering

Original sludge from wastewater treatment plants (WWTPs) usually has a poor dewaterability. Conventionally, mechanical dewatering methods are used to increase the dry solids (DS) content of the sludge. However, sludge dewatering is an important economic factor in the operation of WWTPs, high water content in the final sludge cake is commonly related to an increase in transport and disposal costs. Electro‐dewatering could be a potential technique to reduce the water content of the final sludge cake, but the parameters affecting the performance of electro‐dewatering and the quality of the resulting sludge cake, as well as removed water, are not sufficiently well known. In this research, non‐pressure and pressure‐driven experiments were set up to investigate the effect of various parameters and experimental strategies on electro‐dewatering. Migration behaviour of organic compounds and metals was also studied. Application of electrical field significantly improved the dewatering performance in comparison to experiments without electric field. Electro‐dewatering increased the DS content of the sludge from 15% to 40 % in non‐pressure applications and from 8% to 41% in pressure‐driven applications. DS contents were significantly higher than typically obtained with mechanical dewatering techniques in wastewater treatment plant. The better performance of the pressure‐driven dewatering was associated to a higher current density at the beginning and higher electric field strength later on in the experiments. The applied voltage was one of the major parameters affecting dewatering time, water removal rate and DS content of the sludge cake. By decreasing the sludge loading rate, higher electrical field strength was established between the electrodes, which has a positive effect on an increase in DS content of the final sludge cake. However interrupted voltage application had anegative impact on dewatering in this study, probably because the off‐times were too long. Other factors affecting dewatering performance were associated to the original sludge characteristics and sludge conditioning. Anaerobic digestion of the sludge with high pH buffering capacity, polymer addition and freeze/thaw conditioning had a positive impact on dewatering. The impact of pH on electro‐dewatering was related to the surface charge of the particles measured as zeta‐potential. One of the differences between electro‐dewatering and mechanical dewatering technologies is that electro‐dewatering actively removes ionic compounds from the sludge. In this study, dissolution and migration of organic compounds (such as shortchain fatty acids), macro metals (Na, K, Ca, Mg, Fe) and trace metals (Ni, Mn, Zn, Cr) was investigated. The migration of the metals depended on the fractionation and electrical field strength. These compounds may have both negative and positive impacts on the reuse and recycling of the sludge and removed water. Based on the experimental results of this study, electro‐dewatering process can be optimized in terms of dewatering time, desired DS content, power consumption and chemical usage.

Removal of organic matter and nutrients from slaughterhouse wastewater by using Eichhornia crassipes and evaluation of the generated biomass composting

The objective of this research was to evaluate the performance of the aquatic macrophyte Eichhornia crassipes applied in situ in a slaughter house treatment system, located in the west of the Paraná state, Brazil, regarding the nutrients removal and organic matter. Moreover, it aimed to obtain data from the production, management and composting practices of the biomass generated in the system. During 11 months of macrophytes development, physic and chemical parameters were monitored and plant density was controlled by periodical removal of excess biomass, which was weekly monitored and it is expressed in kg of aquatic plant per m² covered area. The degradation of the macrophytes removed from the treatment system was evaluated at the pilot scale in eight composting piles of 0.60 m³ that underwent four different treatments and two repetitions: T1 - water hyacinth (Eichhornia crassipes); T2 - water hyacinth and swine excrement (7:1), T3 - water hyacinth, swine excrement and earth (7:1:0,67), and T4 - water hyacinth, swine excrement and cellulosic gut (7:1:0,67), for a period of 90 days. The results indicated maximum removal efficiencies of 77.2% for COD; 77.8% for BOD, 87.9% for total nitrogen, 47.5% for ammonia nitrogen and 38.9% for total phosphorus for a five-day retention time. For biomass stabilization by composting, considering the C:N ratio as an indicator of compost maturity, it was observed that treatment T4 resulted in the shortest stabilization period (60 days). No difference was verified in the biostabilization rates at 5% level by the F test.

Ammonia nitrogen desorption from sanitary landfill leachate in filling towers

Sanitary landfill leachates present high concentrations of carbonaceous and nitrogenous materials. The crucial point is that carbonaceous materials are of difficult biodegradation, what compromises the performance of biological treatment processes, while nitrogenous materials, such as ammonia nitrogen, probably preclude the use of biological treatments. Therefore, the aim of this work was to study the desorption process of ammonia nitrogen from sanitary landfill leachate in filling towers. Desorption was carried out in filling towers of 35 L capacity. The leachate was collected from a sanitary landfill located in João Pessoa, Paraíba State, Brazil. Desorption efficiency for the pH values ​​adopted in four treatments was 93% minimum and 95.5% maximum, with aeration mean time ranging from 3 to 6 hours. The limiting factors of ammonia nitrogen desorption from sanitary landfill leachates in filling towers are associated with the use of alkalizer species for pH correction, and electricity costs for aeration.

Magnesium hydroxide-based peroxide bleaching of high-brightness mechanical pulps

A high final brightness is desired in most paper and board products. This requires bleaching processes that are able to produce high-brightness pulps. Mechanical pulps are widely bleached for high brightness using alkaline hydrogen peroxide with traditional sodium hydroxide and sodium silicate as additives. With high doses however, peroxide bleaching causes high organic loads in the mill effluent and anionic trash carry-over to papermaking. To alleviate the problems that arise from the use of sodium-based additives in peroxide bleaching, interest in the use of alternative magnesium-based chemicals has increased. In this study, a new, technical high-purity magnesium hydroxide-based bleaching additive was evaluated on laboratory-scale, pilot-scale and mill-scale experiments and trials for its ability to produce a high brightness in peroxide bleaching without the known problems of sodium-based chemicals. The key findings of this study include: a high brightening potential of peroxide bleaching using the Mg(OH)2-based additive, significant reductions (40-70%) in all categories of environmental load, and cationic demand lowered by 60-70% in bleached pulp with no loss in strength properties or in sheet bulk. When used in TMP refiner bleaching, the Mg(OH)2-based additive resulted in savings in specific energy consumption and provided a good bleaching response.

Optimization and validation of the solid-liquid extraction technique for determination of picloram in soils by high performance liquid chromatography

The objective of this study was to optimize and validate the solid-liquid extraction (ESL) technique for determination of picloram residues in soil samples. At the optimization stage, the optimal conditions for extraction of soil samples were determined using univariate analysis. Ratio soil/solution extraction, type and time of agitation, ionic strength and pH of extraction solution were evaluated. Based on the optimized parameters, the following method of extraction and analysis of picloram was developed: weigh 2.00 g of soil dried and sieved through a sieve mesh of 2.0 mm pore, add 20.0 mL of KCl concentration of 0.5 mol L-1, shake the bottle in the vortex for 10 seconds to form suspension and adjust to pH 7.00, with alkaline KOH 0.1 mol L-1. Homogenate the system in a shaker system for 60 minutes and then let it stand for 10 minutes. The bottles are centrifuged for 10 minutes at 3,500 rpm. After the settlement of the soil particles and cleaning of the supernatant extract, an aliquot is withdrawn and analyzed by high performance liquid chromatography. The optimized method was validated by determining the selectivity, linearity, detection and quantification limits, precision and accuracy. The ESL methodology was efficient for analysis of residues of the pesticides studied, with percentages of recovery above 90%. The limits of detection and quantification were 20.0 and 66.0 mg kg-1 soil for the PVA, and 40.0 and 132.0 mg kg-1 soil for the VLA. The coefficients of variation (CV) were equal to 2.32 and 2.69 for PVA and TH soils, respectively. The methodology resulted in low organic solvent consumption and cleaner extracts, as well as no purification steps for chromatographic analysis were required. The parameters evaluated in the validation process indicated that the ESL methodology is efficient for the extraction of picloram residues in soils, with low limits of detection and quantification.

Potential of macrophytes for removing atrazine from aqueous solution

The potential of three macrophytes, Azolla caroliniana, Salvinia minima, and Lemna gibba was assessed in this study to select plants for use in environmental remediation contaminated with atrazine. Experiments were carried out in a greenhouse over six days in pots containing Hoagland 0.25 strength nutritive solution at the following atrazine concentrations: 0; 0.01; 0.1; 1.0; 10.0 mg L-1. Decrease in biomass accumulation was observed in the three macrophytes, as well as toxic effects evidenced by the symptomatology developed by the plants which caused their deaths. The chlorosis and necrosis allowed to observe in the plants the high sensitivity of the three species to the herbicide. Plants presented low potential for removal of atrazine in solution when exposed to low concentrations of the herbicide. However, at the 10.0 mg L-1 atrazine concentration, L. gibba and A. caroliniana showed potential to remove the herbicide from the solution (0.016 and 0.018 mg atrazine per fresh mass gram, respectively). This fact likely resulted from the processes of atrazine adsorption by the dead material. The percentage of atrazine removed from the solution by the plants decreased when the plants were exposed to high concentrations of the pollutant. Azolla caroliniana, S. minima, and L. gibba were not effective in removing the herbicide from solution. The use of these species to remedy aquatic environments was shown to be limited.

Potential of macrophyte for removing arsenic from aqueous solution

The potential of three aquatic macrophytes, Azoll caroliniana, Salvinia minima and Lemna gibba, was evaluated in this work aimed at selection of plants to be used in remediation of environments contaminated by arsenic (As). The experiments were carried out in a greenhouse during six days in pots containing Hoagland solution (¼ ionic strength) at As concentrations of 0.5; 2.5 and 5.0 mg L-1. The three species showed greater As accumulation as the concentration of the metalloid in solution increased. However, a reduction was detected in fresh and dry mass gain when the plants were exposed to high As concentrations. The macrophytes showed differences in efficiency of removal of As in solution. A. caroliniana, S. minima and L. gibba accumulated, on average, 0.130; 0.200; and 1.397 mg mDM-1, respectively, when exposed to 5.0 mg L-1 of As. The macrophytes absorbed a greater quantity of As in solution with low phosphate content. The greater As concentration in L. gibba tissues lowered the chlorophyll and carotenoid contents as shown by the high chlorosis incidence. Lemna gibba also exhibited a decrease in leaf size, with the total chlorophyll and carotenoid synthesis not being affected by As in A. caroliniana. This species exhibited purplish leaves with high concentration of anthocyanin, whose presence suggested association to phosphate deficiency. Marginal necrosis occurred on S. minima floating leaves, with the released daughter-plants not showing any visual symptoms during the treatment. The percentage of As removed from the solution decreased when the plants were exposed to high concentrations of the pollutant. Among the three species studied, only L. gibba could be considered an As hyper-accumulator. The use of this plant species for remediation of aquatic environments was shown to be limited and requires further investigation.