This diploma thesis deals with the study of adsorption of low-molecular components of organic substances produced by phytoplankton - AOM (Algal Organic Matter) on AC (Activated Carbon) during drinking water treatment. For the experimental purpose in this thesis, there were used selected amino acids as low molecular substances of AOM that are difficult to remove by conventional water treatment process by coagulation. As adsorbent, there was used a detailed characterized of granulated activated carbon (GAC) - Filtrasorb TL 830 (FTL830) which is intended directly for the purpose of water treatment. There were realizing the equilibrium batch adsorption experiments with three different model amino acids - arginine (Arg), phenylalanine (Phe) and aspartic acid (Asp). There was investigated the efficiency of removing amino acid depending on the solution temperature and pH. Results of the adsorption experiments have shown that the temperature affects the adsorption efficiency. Adsorption is essentially described as an exothermic process but the adsorption of Arg and Phe from an aqueous solution to GAC occurs more efficiently at higher temperatures. It means that the adsorption is the endothermic process. In the case of Arg adsorption, the temperature was found to influence adsorption efficiency less than...

<p>U&nbsp; radu&nbsp; je&nbsp; ispitan&nbsp; uticaj&nbsp; amida&nbsp; kao&nbsp; modela&nbsp; AOM-a (Algalne organske materije)&nbsp; na adsorpciju nitrofenola iz vodene&nbsp; sredine&nbsp; na&nbsp; aktivnom&nbsp; uglju.&nbsp; Istraţivanje&nbsp; se sastojalo&nbsp; iz&nbsp; tri&nbsp; faze:&nbsp; ispitivanje&nbsp; uticaja&nbsp; karateristika amida&nbsp; na&nbsp; adsorpciju&nbsp; nitrofenola,&nbsp; ispitivanje&nbsp; uticaja granulacije na adsorpciju nitrofenola u prisustvu amida i ispitvanje karakterisitka samih nitrofenola na adsorpciju u&nbsp; prisustvu&nbsp; amida.&nbsp; Pre&nbsp; ispitivanja&nbsp; adsorpcije&nbsp; u dvokomponentnim&nbsp; sistemima&nbsp; ispitana&nbsp; je&nbsp; adsorpcija jednokomponentnih&nbsp; sistema&nbsp; 4-nitrofenola,&nbsp; 2,4-dinitrofenola&nbsp; i&nbsp; 2,4,6-trinitrofenola,&nbsp; kao&nbsp; i&nbsp; amida&nbsp; Nmetilbenzamid,&nbsp; nikotinamida&nbsp; i&nbsp; N-benzilbenzamida&nbsp; na komercijalnim&nbsp; aktivnim&nbsp; ugljevima&nbsp; NORIT&nbsp; SA2&nbsp; i&nbsp; dve granulacije&nbsp; aktivnog&nbsp; uglja&nbsp; DARCO.&nbsp; Aktivni&nbsp; ugljevi&nbsp; su ispitani&nbsp; metodom&nbsp; FTIR&nbsp; spektroskopije,&nbsp; SEM&nbsp; analizom, analizom&nbsp; povr&scaron;ine&nbsp; adsorpcijom&nbsp; azota&nbsp; na&nbsp; niskoj temperaturi&nbsp; i&nbsp; određivanjem&nbsp; taĉke&nbsp; nultog&nbsp; naelektrisanja. Urađena&nbsp; je&nbsp; geometrijska&nbsp; optimizacija&nbsp; modela&nbsp; molekula ispitivanih nitrofenola i amida i izraĉunati su molekulski parametri.&nbsp; Uticaj&nbsp; amida&nbsp; kao&nbsp; modela&nbsp; AOM-a&nbsp; je&nbsp; ispitan kori&scaron;ćenjem&nbsp; razliĉitih&nbsp; ravnotežnih&nbsp; i&nbsp; difuzionih adsorpcionih&nbsp; modela.&nbsp; Kao&nbsp; kriterijum&nbsp; za&nbsp; određivanje najsporije&nbsp; adsorpcione&nbsp; faze&nbsp; kori&scaron;ćen&nbsp; je&nbsp; Biotov&nbsp; broj.<br />Adsorpcioni&nbsp; parametri&nbsp; dobijeni&nbsp; u&nbsp; eksperimentima&nbsp; sa dvokomponentnim&nbsp; sistemima&nbsp; su&nbsp; upoređivani&nbsp; sa parametrima dobijenim za adsorpciju samih nitrofenola.</p> / <p>In this research influence of selected amides, as a model of&nbsp; AOM&nbsp; (Algal&nbsp; organic&nbsp; matter),&nbsp; on&nbsp; adsorption&nbsp; of nitrophenols&nbsp; from&nbsp; water&nbsp; on&nbsp; activated&nbsp; carbon&nbsp; has&nbsp; been<br />investigated.&nbsp; Research&nbsp; is&nbsp; divided&nbsp; in&nbsp; three&nbsp; phases: investigation&nbsp; of&nbsp; influence&nbsp; of&nbsp; amide&nbsp; molecule characteristics&nbsp; on&nbsp; the&nbsp; adsorption&nbsp; of&nbsp; nitrophenols, investigation&nbsp; of&nbsp; granulation&nbsp; influence&nbsp; on&nbsp; nitrophenol adsorption in&nbsp; the&nbsp; presence of amide and investigation of nitrophenol characteristics that can influence adsorption in&nbsp; the&nbsp; presence&nbsp; of&nbsp; amides.&nbsp; Adsorption&nbsp; of&nbsp; nitrophenols and&nbsp; amides&nbsp; in&nbsp; single- component&nbsp; systems&nbsp; has&nbsp; also&nbsp; been carried&nbsp; out.&nbsp; Adsorption&nbsp; kinetics&nbsp; of&nbsp; 4-nitrophenol,&nbsp; 2,4-dinitrophenol,&nbsp; 2,4,6-trinitrophenol,&nbsp; N-methylbenzamide,<br />nicotinamide&nbsp; and&nbsp; N-benzylbenzamide&nbsp; has&nbsp; also&nbsp; been investigated. Commercial activated carbons NORIT SA2 and&nbsp; two&nbsp; granulations&nbsp; of&nbsp; DARCO&nbsp; were&nbsp; used.&nbsp; Activated carbons&nbsp; were&nbsp; characterized&nbsp; using&nbsp; FTIR&nbsp; spectroscopy, SEM&nbsp; analysis,&nbsp; internal&nbsp; surface&nbsp; analysis&nbsp; using&nbsp; nitrogen adsorption&nbsp; on&nbsp; low&nbsp; temperature&nbsp; and&nbsp; determination&nbsp; of point&nbsp; of&nbsp; zero&nbsp; charge.&nbsp; Geometry&nbsp; optimization&nbsp; of nitrophenol&nbsp; and&nbsp; amide&nbsp; molecules&nbsp; has&nbsp; been&nbsp; carried&nbsp; out and different molecular parameters have been calculated. Influence&nbsp; of&nbsp; amides&nbsp; as&nbsp; AOM&nbsp; model&nbsp; has&nbsp; been investigated by using diffusion and equilibrium models. Biot number has been obtained&nbsp; in order to establish the limiting&nbsp; step&nbsp; in&nbsp; adsorption&nbsp; process.&nbsp;&nbsp; Adsorption parameters&nbsp; obtained&nbsp; in&nbsp; two-component&nbsp; adsorption systems&nbsp; were&nbsp; compared&nbsp; to&nbsp; parameters&nbsp; obtained&nbsp; for adsorption of nitrophenols alone.</p>

The diploma thesis is aimed at adsorption processes during the removal of pesticides onto granular activated carbon (GAC) in the process of drinking water treatment. Adsorption onto GAC represents an efficient method for pesticides removal. High adsorption efficiency can be significantly reduced due to the occurrence of natural organic matter (NOM) in raw water, which involves AOM (Algal Organic Matter) produced by phytoplankton. Analogous to NOM, AOM probably affects adsorption of pesticides by two different mechanisms - a direct site competition and pore blockage effect, in dependence on the different molecular weight of particular AOM fractions. Equilibrium batch and kinetic adsorption experiments were performed using two types of GAC (Norit 1240 and Filtrasorb 400) and two pesticides (terbuthylazine and alachlor). In order to examine the effect of AOM on adsorption of pesticides, raw GAC and GAC preloaded by AOM were used. The effect of pH on the competitive adsorption of AOM was also evaluated. A solid phase extraction (SPE) method and gas chromatography with electron capture detection (GC-ECD) were used to determine pesticides in water samples. AOM was characterized using fractionation onto sorptive resins. The representation of apparent molecular weights of AOM proteins was determined by...

There is a current lack of accurate tools to determine the concentration of cyanobacteria in situ.  Besides, cyanobacterial blooms have to be carefully monitored in reservoirs as they are more frequent because of climate change and can lead to potential released of toxins, along with other components. This project investigates the possible use of fluorescent probes to measure the concentration of different types of organic matter released by the algae. Three different species of toxic cyanobacteria were chosen to carry out this research as they are representative of the local harmful blooms found across Australia. Furthermore, the efficiency of two different chemicals (powdered activated carbon, also known as PAC, and alum) used in drinking water treatment plants were investigated, in order to determine a method for automatic dosage adjustment in water treatment plant. The organic matter was characterized by LC-OCD and fluorescence spectroscopy and statistical analysis such as principal component analysis was performed on the generated data. General characterization of the different species was firstly performed and globally, similar comportments were observed among the three cyanobacteria species. There is indeed a general increase in the release of organic material throughout the cell’s growth phase. Results from the jar tests showed that PAC mainly targeted humic-like substances and building blocks, which are middle size particles. The average removal rate obtained was 40µg/L per mg/L of PAC added into the water. Therefore, there is indication that the decreased efficiency for the removal of the taste and odor compounds observed in certain plants can be partially attributed to direct competition of organic matter adsorption onto PAC instead of a blockage of the PAC pores by larger particles. On the other hand, alum was able to remove large particles, particularly biopolymers and also humic-substances. However, a great increase of the low molecular weight molecules at very high doses of alum was seen, which suggest that a too high dose of alum is toxic for the algae cells. Based on the bench scale testing the recommended dose of 50 mg/L seems to be optimum for the studied water treatment plant. Specific ultraviolet absorbance and dissolved organic carbon measurements were also investigated and good correlations were found between the concentration of humic-like substances and absorbance, confirming that they are good measure to assess the content of organic matter in the water. However, as the slope coefficient of the linear trend varied between the species, it was not possible to obtain a common conversion factor for all the species. Finally, one fluorophore was found in common to all the samples and is characterized by the excitation-emission wavelength: 240/440 nm. Correlations with the chromatography’s results were investigated and this component seems to match the biopolymers and humic-like substances concentrations. Furthermore, its intensity decreases continuously with the addition of PAC whereas a drop was observed at the lower doses of alum. In regards on these findings, a method for automatic chemicals dosing from the fluorescence measures was proposed. / Detta examensarbete handlar om hur dricksvattenkvalitet kan kontrolleras och övervakas i vattenreningsverk. Nu existerar  inte någon exakt metod för att bestämma koncentrationen av cyanobakterier i vatten då det finns många olika arter. Men det är viktigt att övervaka algers tillväxt in i vattenreningsverk för de kan släppa ut skadliga ämnen till dricksvattnet. De tre arter som studerats i detta projekt är giftiga. Det organiska materialet i råvattnet kan också blockera membranporer eller leda till n biprodukter, som är cancerframkallande. Till sist konkurrerar några organiska substansen med smak- och luktföreningar för adsorptionsställena hos det pulverformiga aktiverade kolet. Därför är smaken och luktföreningarna inte väl borttagna, vilket leder till kundernas klagomål. Cyanobakterier måste övervakas noggrant.                            För att bestämma biologisk och kemisk egenskap hos vatten används flera tekniker för närvarande. I examensarbetet har undersökningar med vätskekromatografi och fluorescensteknik företagits. Kromatografi användes för att klassificera den organiska substansen i mindre grupper: biopolymerer, humus substanser, byggstenar och neutralmolekyler med låg molekylvikt (LMVN). Statistisk analys med R, inklusive huvudkomponentanalys företogs på insamlade data. Fluorescensdata registrerades också och visas i en excitationsutsläppsmatris.                            Experimenten reproducerade en behandlingsprocess och undersökte effektiviteten hos två kemikalier: pulveriserat aktivt kol (PAK) och alun. Resultaten visade att humusämnen   och dess byggstenar var väl borttagna av PAK medan även biopolymerer och humusämnen var väl bortagna av alun. Emellertid var en för hög dos av alun skadlig eftersom det ledde till en ökad frisättning av LMVN. I synnerhert kunde PAK ta bort 40µg/L av både humusämnen och dess byggstenar per mg/L av PAK tillagd. Det föreslår att de är de viktigaste konkurrenterna och att endast direkt konkurrens för adsorptionsställena sker. Om det fanns blockeringsfenomen, skulle det också finnas en minskning för biopolymererna. Den optimala doseringen av alun som bestämdes för det undersökta vattenreningsverket var 50 mg/L. Det kunde ta bort 60-70% av biopolymerer och 40-50% av humusämnen.                            Specifik ultraviolett absorbans och fluorescens registrerades. Båda visade riktigt bra korrelationer med humusämnen, vilket gör de till bra verktyg för att bedöma vattenkvaliteten. Men det kräver fortfarande att arten av cyanobakterie urskiljs eftersom koefficientens lutningar var olika. De kan därför vara ett verktyg för att mäta koncentrationen av organisk material, men arten måste vara känd. Fluorescencedata visade en topp vid 440 nm. En parallellfaktoranalys utfördes på data och endast en komponent hittades gemensam i alla prover. Därför studerades den maximala fluorescensintensiteten hos denna komponent. Å ena sidan kunde vi observera en kontinuerlig minskning av intensiteten när PAK tillsattes. Det är därför möjligt att veta hur man justerar den kemiska doseringen från fluorescensintensiteterna. I slutet av examensarbetet föreslås en metod för automatisk kemisk dosering. Fluorescensprober kan ännu inte exakt indikera cellkoncentrationen. Men med flera sonder som riktar sig till olika våglängder kan de redan vara till stor hjälp för styrning vid vattenverk.

The diploma thesis investigates the coagulation of nature waters with humic substances and peptides/proteins produced by Microcystis aeruginosa during water treatment process with aluminum coagulants. It was confirmed that the efficiency of coagulation mechanism of humic substances and peptides/proteins strongly depends on the pH value, because pH value is limited factor of a charge properties of peptides/proteins, humic substances and hyrolysis products of coagulants. The optimal pH range for the coagulation of humic substances was 5- 6 and for cyanobacterial peptides/proteins 5-6.5. In both cases a charge neutralisation and an adsorption were dominant mechanism of coagulation. Optimal pH range for the coagulation of humic substances in the presence of cyanobacterial peptides/proteins was identical as well as optimal pH range of humic substances with absence of peptides/proteins (5-6) but the presence of peptides/proteins positively influenced particle coagulation of humic substances, because the optimal concentration of the coagulants decreased to more than half. An interaction between humic substances and peptides/proteins was demonstrated. A positive effect of coagulation was observed in the case of jar tests with absence of coagulants at a very low pH range (<4). Keywords Humic substances; AOM...

The aim of the diploma thesis is to analyze the mechanisms involved in the coagulation of peptides and proteins contained in cellular organic matter produced by Microcystis aeruginosa, and to describe their influence on the coagulation of hydrophobic kaolin suspension. According to the results of jar tests, the coagulation effectiveness and removability of COM peptides/proteins and kaolin particles are heavily dependent on pH value which determines charge characteristics of peptides/proteins, kaolin and hydrolysis products of coagulant and therefore the prevailing mechanisms of interactions between them. Efficient coagulation and the highest removal of COM peptides and proteins were achieved in the pH range of 4-6 due to charge neutralization of peptide/protein negative surface by positively charged hydrolysis products of ferric coagulant. Peptides and proteins contributed to the coagulation of kaolin particles under the reaction conditions mentioned above, too. Charge neutralization and adsorption were found to be the dominant coagulation mechanisms under these conditions. At a low COM/Fe concentration ratio (COM/Fe < 0.33), adsorption of peptides/proteins onto ferric oxide-hydroxide particles, described as the electrostatic patch model, enabled the coagulation in the pH range of 6-8. On the...

The aim of this diploma thesis is to evaluate the efficiency of two types of granular activated carbon (GAC), Filtrasorb TL 830 and Picabiol 12x40, for the adsorption of cellular peptides with low molecular weight produced by cyanobacterium Microcystis aeruginosa that are hardly removable during the coagulation/flocculation processes. The effect of different carbon properties (surface charge, textural characteristics), peptide properties (molecular size, surface functionality and charge) and solution characteristics (ionic strength and pH value) on the peptide uptake was investigated using laboratory equilibrium and kinetic adsorption experiments. The results showed that adsorption of peptides was influenced by the charge conditions in adsorption system that depend on solution pH. The pH value influences surface charge and the point of zero charge (pHpzc) of GAC as well as dissociation and protonization of peptide functional groups. It was found that efficiency of the peptide adsorption increased with decreasing pH value for both GACs. Under these conditions adsorption was enhanced by attractive electrostatic interactions between GAC surface and peptide functional groups and was also positively influenced by the conformation changes in peptide structure. GAC Picabiol 12x40 showed the total highest...

6 Abstract: The presence of phytoplankton and its products (AOM) in source water is a current challenge in water treatment processes. The production of AOM increases with anthropogenic eutrophication of ecosystems. AOM impair the water treatment processes and may form harmful disinfection by-products. The traditional water treatment process is a coagulation, which is very efficient in removing phytoplankton cells, but this is not the case when removing some kinds of AOM. Especially its nonproteinaceous fraction with low molecular weight, which can represent majority of total organic carbon, is removed with very low efficiency. The removal of AOM by coagulation can be enhanced by preoxidation. This thesis examines the influence of preoxidation by potassium permanganate of nonproteinaceous fraction of COM of algae Chlorella vulgaris on its coagulation by aluminium sulphate and polyaluminiumchloride. To compare, solutions with nonproteinaceous COM were coagulated with and without preoxidation by five different doses of permanganate (0,025; 0,05; 0,1; 0,15 a 0,2 mg KMnO4 mg-1 DOC). The doses of permanganate and time need for oxidation (30 minutes) were determined by decreased DOC and permanganate during preoxidation experiments. The maximal DOC removals achieved both with and without preoxidation were 17 %...

The dissertation thesis focuses on the application of activated carbon for the removal of low molecular weight algal organic matter (AOM) produced by phytoplankton during drinking water treatment, as well as on the effect of AOM on adsorption of anthropogenic micropollutants contained in raw water. The results of this study have been published in international peer-reviewed journals in 4 papers and in 2 conference contributions. The efficiency of AOM removal was studied in laboratory equilibrium and kinetic experiments using different types of granular activated carbon and cellular peptides with molecular weight < 10 kDa produced by cyanobacterium Microcystis aeruginosa. It has been previously confirmed that these peptides are removed with difficulty during the conventional water treatment based on coagulation/flocculation processes and therefore, other methods need to be applied for their restriction. The effect of solution properties on peptide adsorption was assessed by the tests at different pH values and at variable ionic strengths. The negative impact of peptides on the adsorption of organic micropollutants present in raw water was simulated using competitive adsorption experiments with herbicides alachlor and...

The Ph.D. thesis deals with the characterization of algal organic matter (AOM), which is difficult to remove in water treatment, and on the basis of AOM character, various methods for its elimination, e.g. coagulation, oxidation with subsequent coagulation and adsorption onto activated carbon are assesed. Special emphasis is placed on identifying the optimal conditions of the processes and on describing the mechanisms and interactions involved. In terms of anthropogenic micropollutants, the thesis deals with the highly topical issue of the occurrence of microplastics in water. It was found that the removal efficiency of the individual AOM components varies substantially depending on the elimination method used. The identified optimum conditions of individual methods and especially the mechanisms that apply to the removal of target substances varied widely. The non-proteinaceous fraction of AOM was removed with very low efficiency (max. 25%) by conventional coagulation even under optimized conditions (pH 6.6- 7.5 for aluminium sulfate as the coagulating agent and pH 7.5-9.0 for polyaluminium chloride) and it was given by the high content of low molecular weight (LMW) substances that are difficult to coagulate. The dominant coagulation mechanism was adsorption onto aluminium hydroxide precipitates....