Imatran tehtaiden jätevesipäästöjen hallinta- ja analysointityökalun kehittäminen

Työn tavoitteena oli kehittää Stora Enso Oyj:n Imatran tehtaille Wedge-pohjainen analysointityökalu, jolla voidaan hallita prosessi- ja päästötietojen yhteys nykyistä paremmin. Wedgeen määriteltiin päästömittauksia, olennaisia prosessimittauksia ja tarpeelliset laskennat kuormituksen ennustamiseksi lähtien tuotantoprosessien tilasta. Työssä tehtiin kemialliselle ja biologiselle jätevedenpuhdistamolle meneville jätevesille laskennallisia malleja, joita verrattiin mitattuihin arvoihin. Kemialliselle jätevedenpuhdistamolle meneville jätevesille tehtiin malli jäteveden virtaamalle. Biologiselle jätevedenpuhdistamolle meneville jätevesille tehtiin mallit jäteveden virtaamalle sekä COD-, AOX- ja alkuainekuormituksille. Alkuaineista työhön otettiin mukaan natrium, rikki ja kloori. Teoriaosassa on käsitelty sellu- ja paperitehtaiden vedenkäyttöä, tehtaan eri osastojen jätevesikuormitusta, jäteveden puhdistusmenetelmiä sekä prosessidatan käsittelymenetelmiä. Kokeellisessa osassa on esitelty mitattujen ja laskennallisten mallien yhteyttä. Suurin osa laskennallisista malleista näyttää seuraavan kohtuullisen hyvin mitattuja arvoja. Kokeellisessa osassa on myös havainnollistettu esimerkkien avulla mallien hyödyntämistä. Työn hyötynä on normaalien kuormitusvaihteluiden ja häiriöpäästöjen entistä tarkempi ja nopeampi erottelu. Pitkällä tähtäimellä Wedge-ohjelman avulla pystytään keskittämään jätevesikuormituksen vähentämistoimenpiteet olennaisimpiin kohteisiin.

Uso da pressão gerada por uma coluna de água para controle da vazão em sistemas de análises em fluxo

This work presents a new approach to control the flow rate in hydrodynamic flow experiments. The combination of air pressure generated by an aquarium air pump and the pressure generated by a water column were used for this purpose. This device supports a stable flow rate without pulsation for a long period of time. Furthermore, the flow rate can be easily controlled at various values in one or more streams. The performance of this approach was investigated using Fe(CN)6(4-) solutions in flowing systems using amperometric and voltammetric detection in wall-jet configuration. The results showed that the performance of the proposed device was better than a commercial peristaltic pump. It suggests that this approach can be used successfully in flow analysis systems.

Vedenlaadun parantamismahdollisuudet virtausohjauksen avulla läntisen Pien-Saimaan tapauksessa

Läntisen Pien-Saimaan vesistön alueella on ilmennyt voimakasta sinileväkukintaa vuosina 2006 - 2009. Yksi tehokas keino vähentää sinilevien määrää ja parantaa vedenlaatua, onravinnepitoisuuksien alentaminen virtausohjauksen avulla. Tästä on 70 vuoden kokemus Pien- Saimaan itäosissa, joissa Vehkataipaleen pumppaamon virta on pitänyt vedenlaadun hyvänä huolimatta vesialuetta raskaasti rasittavasta puunjalostusteollisuudesta. Diplomityössä selvitetään mahdollisuuksia toteuttaa virtauksenohjausta myös läntisen Pien-Saimaan puolella, jolloin tavoitteena on vedenlaadun paraneminen. Vedenlaadun parantamista edellyttää myös Euroopan unionin vesipuitedirektiivi. Selvityksessä tarkasteltiin virtauksenohjauksen eri toteutusvaihtoehtoja ja arvioitiin näiden vaikutuksia eri alueiden vedenlaatuun. Tämän lisäksi kartoitettiin ja arvioitiin eri vaihtoehdoista aiheutuvia riskejä. Näiden tietojen pohjalta päädyttiin suositeltaviin virtauksenohjauksen toteutusvaihtoehtoihin, joita ovat Kolhonlahti – Kolinlahti välillä toteutettu pumppaus ja mahdollisen Kutilan kanavan rakentamisen yhteydessä Kopinsalmen pumppaamo. Kolhonlahti – Kolinlahti sijaitsee Pien-Saimaan koillisosassa lähellä Rehulaa. Muista tarkastelluista kohteista saatiin yhdistelemällä suositeltavaksi vaihtoehdoksi myös Vehkataipaleen pumppaamon virran kasvattaminen yhdistettynä Kirjamoinsalmen tai Kopinsalmen pumppaamoon. Tämän lisäksi eri vaihtoehdoille laadittiin alustava kustannustarkastelu. Selvityksessä käytettyjä menetelmiä ja tuloksia voidaan soveltaa myös muihin vastaavan tyyppisiin vesistöjen kunnostushankkeisiin. Työssä on lisäksi koottu yhteen yleistietoja Pien-Saimaasta ja sen tunnetuista virtauksista.

Determination of etoricoxib in human plasma using automated on-line solid-phase extraction coupled with LC-APCI/MS/MS

A liquid chromatography-tandem mass spectrometry method with atmospheric pressure chemical ionization (LC-APCI/MS/MS) was validated for the determination of etoricoxib in human plasma using antipyrin as internal standard, followed by on-line solid-phase extraction. The method was performed on a Luna C18 column and the mobile phase consisted of acetonitrile:water (95:5, v/v)/ammonium acetate (pH 4.0; 10 mM), run at a flow rate of 0.6 mL/min. The method was linear in the range of 1-5000 ng/mL (r²>0.99). The lower limit of quantitation was 1 ng/mL. The recoveries were within 93.72-96.18%. Moreover, method validation demonstrated acceptable results for the precision, accuracy and stability studies.

Estudo da degradação de ranitidina via H2O2 eletrogerado/Fenton em um reator eletroquímico com eletrodos de difusão gasosa

The study of the electrochemical degradation of the ranitidine was developed using an electrochemical reactor with a gas diffusion electrode (GDE) as cathode. The electrolysis experiments was performed at constant current (1 < A < 10) and flow rate of 200 L h-1. The process of drug degradation, chemical/electrochemical and electro-Fenton ways, using electrochemical reactor showed best efficiency at current values of > 4 A. The process reached a production of 630 mg L-1 of the H2O2 at 7 A. The ranitidine concentrations was reduced in 99.9% (HPLC) and chemical oxygen demand (COD) was reduced in 86.7% by electro-Fenton.

Desenvolvimento e validação de um método analítico rápido por cromatografia líquida de alta eficiência para determinação de nimesulida em estudos de liberação in vitro

A high performance liquid chromatography (HPLC) method has been developed for a rapid determination of nimesulide in dissolution studies. Nimesulide was analyzed using 5 µm Lichrospher® RP-18 column (125 x 4 mm i.d.) and mobile phase acetonitrile: phosphate buffer pH=6.0 (55:45) at a flow-rate of 1.0 mL min-1. Detection was carried out at 300 nm at 25 ºC. The method was applied to analysis of nimesulide in in vitro release studies and showed a rapid and efficient analytical alternative for evaluation of dissolution profile of nimesulide.

Removal of phenol and conventional pollutants from aqueous effluent by chitosan and chitin

The present study deals with phenol adsorption on chitin and chitosan and removal of contaminants from wastewater of a petroleum refinery. The adsorption kinetic data were best fitted to first- and second-order models for chitosan and chitin, respectively. The results of adsorption isotherms showed Langmuir model more appropriately described than a Freundlich model for both adsorbents. The adsorption capacity was 1.96 and 1.26 mg/g for chitin and chitosan, respectively. Maximum removal of phenol was about 70-80% (flow rate: 1.5 mL/min, bed height: 18.5 cm, and 30 mg/L of phenol. Wastewater treatment with chitin in a fixed-bed system showed reductions of about 52 and 92% for COD and oil and greases, and for chitosan 65 and 67%, respectively. The results show improvement of the effluent quality after treatment with chitin and chitosan.

Determination of phenobarbital in human plasma by a specific liquid chromatography method: application to a bioequivalence study

A liquid chromatography method was developed and validated for the determination of phenobarbital in human plasma using phenytoin as internal standard. The drugs were extracted from plasma by liquid-liquid extraction and separated isocratically on a C12 analytical column, maintained at 35 ºC, with water:acetonitrile:methanol (58.8:15.2:26, v/v/v) as mobile phase, run at a flow rate of 1.2 mL/min with detection at 205 nm. The method was linear in the range of 0.1-4 μg/mL (r²=0.9999) and demonstrated acceptable results for the precision, accuracy and stability studies. The method was successfully applied for the bioequivalence study of two tablet formulations (test and reference) of phenobarbital 100 mg after single oral dose administration to healthy human volunteers.

Determinação de citrato de sildenafila e de tadalafila por cromatografia líquida de ultraeficiência com detecção por arranjo de diodos (CLUE-DAD)

A simple ultra-performance liquid chromatographic method for the simultaneous determination of sildenafil citrate and tadalafil was developed and validated. Sample preparation was dissolution in methanol, followed by centrifugation and dilution (1:10) with methanol. Analysis was performed in an Acquity® UPLC system with Acquity® BEH C18 column (2.1 x 50 mm, with 1.7 μm particles). The elution was isocratic with phosphate buffer pH 2.3 and acetonitrile (65:35, v/v) at a flow rate of 0.7 mL/min. The method presented adequate specificity, linearity, precision and accuracy and allowed the determination of the drugs in seized forensic samples.

Estudo da eficiência de degradação de tetracloreto de carbono por plasma térmico e caracterização dos produtos formados

Decomposition of carbon tetrachloride in a DC thermal plasma reactor was investigated in argon atmosphere. The operational parameters such as plasma torch power and argon flow rate versus CCl4 conversion were examined. The CCl4 net degradation was determined by GC-FID, the chlorine produced was quantified by iodometric titration, the solid carbon was characterised by Raman spectroscopy and by BET analysis. The solid carbon collected inside de plasma reactor was submitted to solid/liquid extraction and the desorbed species were identified by GC-MS.

Determination of free urinary cortisol in cushing's syndrome using reversed-phase high performance liquid chromatography

Determination of free urinary cortisol is a test of choice in the diagnosis of Cushing's syndrome. In this study, cortisol was quantified using reversed-phase high-performance liquid chromatography (RP-HPLC) in urine samples previously extracted with ether and using triamcinolone acetonide as internal standard (IS). A BDS-Hypersil-C18® column, water-acetonitrile (72:28; v/v), with a flow rate of 1.0 mL/min and detection at 243 nm were used. This method showed to be both effective and efficient, with sensitivity and linearity ranging from 2.50 to 150 μg/L, and can be used in substitution to the radioimmunoassay technique within this concentration range.

Development and validation of a LC-method for the determination of phenols in a pharmaceutical formulation containing extracts from Stryphnodendron adstringens

A sensitive RP-HPLC method with UV detection successfully measured phenol(s) in an ointment containing 3% Stryphnodendron adstringens extract. Chromatography used acetonitrile (0.05% trifluoroacetic acid):water (0.05% trifluoroacetic acid) (v/v), flow rate 0.8 mL min-1. Quantitation was accomplished by the external-standard method. Linearity for 2.00 to 16.00 μg mL-1 (gallic acid) and 1.14 to 18.24 μg mL-1 (gallocatechin) was established. Intra- and inter-day precision levels were under 5%. LOD and LOQ were 0.231 and 0.770 μg mL-1 (gallic acid) and 0.151 and 0.504 μg mL-1 (gallocatechin), respectively. Determination of phenols was unaffected by product excipients.

Terbinafine: optimization of a LC method for quantitative analysis in pharmaceutical formulations and its application for a tablet dissolution test

A simple liquid chromatographic method was optimized for the quantitative determination of terbinafine in pharmaceutical hydroalcoholic solutions and tablets, and was also employed for a tablet dissolution test. The analysis was carried out using a RP-C18 (250 mm × 4.6 mm, 5 μm) Vertical® column, UV-Vis detection at 254 nm, and a methanol-water (95:5, v/v) mobile phase at a flow-rate of 1.2 mL min-1. Method validation investigated parameters such as linearity, precision, accuracy, robustness and specificity, which gave results within the acceptable range. The tablets dissolution was quite fast: 80% of the drug was dissolved within 15 min.

Análise por injeção em fluxo com detecção amperométrica de múltiplos pulsos: potencialidades e aplicações

The potentialities and applications of the Multiple Pulse Amperometric detection (MPA) coupled with Flow Injection Analysis (FIA) are evaluated. Important aspects as cleaning and activation of electrode surface, indirect and simultaneous analysis of electroactive compounds and the use of the internal standard method for quantifications utilizing FIA-MPA are presented. The main parameters concerning the detection of electroactive analytes by multiple pulse amperometric detection in flowing solutions were also discussed. In addition, aspects such as flow rate, sample volume, application time of the potential pulses and instrumentation necessary for implementing of the method were also addressed.

Development and validation of a stability-indicating HPLC method for the determination of buclizine hydrochloride in tablets and oral suspension and its application to dissolution studies

A method using liquid chromatography has been developed and validated for determination of buclizine in pharmaceutical formulations and in release studies. Isocratic chromatography was performed on a C18 column with methanol:water (80:20 v/v, pH 2.6) as mobile phase, at a flow rate of 1.0 mL/min, and UV detection at 230 nm. The method was linear, accurate, precise, sensible and robust. The dissolution test was optimized and validated in terms of dissolution medium, apparatus agitation and rotation speed. The presented analytical and dissolution procedures can be conveniently adopted in the quality and stability control of buclizine in tablets and oral suspension.