Electrochemical evidence of sulfinic acid derivative as an intermediate in the reduction of aromatic sulfonyl chloride in an aprotic medium

The electrochemical reduction of p-nitrobenzenesulfonyl chloride (NBSCl) in dimethylsulfoxide (DMSO) solution is used here as a model to investigate the role of sulfinic acid derivative in this compound's global reduction process. Cyclic voltammetric experiments reveal the production of sulfinic acid derivative, which is important in chemical reactions involving the original compound and other intermediates. This paper also discusses the probable mechanisms of the reduction.

Role of oxidation-reduction cycle of iron in direct leaching of zinc concentrate

Direct leaching is an alternative to conventional roast-leach-electrowin (RLE) zinc production method. The basic reaction of direct leach method is the oxidation of sphalerite concentrate in acidic liquid by ferric iron. The reaction mechanism and kinetics, mass transfer and current modifications of zinc concentrate direct leaching process are considered. Particular attention is paid to the oxidation-reduction cycle of iron and its role in direct leaching of zinc concentrate, since it can be one of the limiting factors of the leaching process under certain conditions. The oxidation-reduction cycle of iron was experimentally studied with goal of gaining new knowledge for developing the direct leaching of zinc concentrate. In order to obtain this aim, ferrous iron oxidation experiments were carried out. Affect of such parameters as temperature, pressure, sulfuric acid concentration, ferrous iron and copper concentrations was studied. Based on the experimental results, mathematical model of the ferrous iron oxidation rate was developed. According to results obtained during the study, the reaction rate orders for ferrous iron concentration, oxygen concentration and copper concentration are 0.777, 0.652 and 0.0951 respectively. Values predicted by model were in good concordance with the experimental results. The reliability of estimated parameters was evaluated by MCMC analysis which showed good parameters reliability.

The Effects of Some Furnish and Paper Structure Related Factors on Wet Web Tensile and Relaxation Characteristics

The objective of this thesis was to identify the effects of different factors on the tension and tension relaxation of wet paper web after high-speed straining. The study was motivated by the plausible connection between wet web mechanical properties and wet web runnability on paper machines shown by previous studies. The mechanical properties of wet paper were examined using a fast tensile test rig with a strain rate of 1000%/s. Most of the tests were carried out with laboratory handsheets, but samples from a pilot paper machine were also used. The tension relaxation of paper was evaluated as the tension remaining after 0.475 s of relaxation (residual tension). The tensile and relaxation properties of wet webs were found to be strongly dependent on the quality and amount of fines. With low fines content, the tensile strength and residual tension of wet paper was mainly determined by the mechanical interactions between fibres at their contact points. As the fines strengthen the mechanical interaction in the network, the fibre properties also become important. Fibre deformations caused by the mechanical treatment of pulp were shown to reduce the mechanical properties of both dry and wet paper. However, the effect was significantly higher for wet paper. An increase of filler content from 10% to 25% greatly reduced the tensile strength of dry paper, but did not significantly impair wet web tensile strength or residual tension. Increased filler content in wet web was shown to increase the dryness of the wet web after the press section, which partly compensates for the reduction of fibrous material in the web. It is also presumable that fillers increase entanglement friction between fibres, which is beneficial for wet web strength. Different contaminants present in white water during sheet formation resulted in lowered surface tension and increased dryness after wet pressing. The addition of different contaminants reduced the tensile strength of the dry paper. The reduction of dry paper tensile strength could not be explained by the reduced surface tension, but rather on the tendency of different contaminants to interfere with the inter-fibre bonding. Additionally, wet web strength was not affected by the changes in the surface tension of white water or possible changes in the hydrophilicity of fibres caused by the addition of different contaminants. The spraying of different polymers on wet paper before wet pressing had a significant effect on both dry and wet web tensile strength, whereas wet web elastic modulus and residual tension were basically not affected. We suggest that the increase of dry and wet paper strength could be affected by the molecular level interactions between these chemicals and fibres. The most significant increases in dry and wet paper strength were achieved with a dual application of anionic and cationic polymers. Furthermore, selectively adding papermaking chemicals to different fibre fractions (as opposed to adding chemicals to the whole pulp) improved the wet web mechanical properties and the drainage of the pulp suspension.

Adsorption isotherm studies of BOD, TSS and colour reduction from palm oil mill effluent (POME) using boiler fly ash

Palm oil is one of the two most important vegetable oils in the world's oil and fats market. The extraction and purification processes generate different kinds of waste generally known as palm oil mill effluent (POME). Earlier studies had indicated the possibility of using boiler fly ash to adsorb impurities and colour in POME treatment. The adsorption treatment of POME using boiler fly ash was further investigated in detail in this work with regards to the reduction of BOD, colour and TSS from palm oil mill effluent. The amount of BOD, colour and TSS adsorbed increased as the weight of the boiler fly ash used was increased. Also, the smaller particle size of 425µm adsorbed more than the 850µm size. Attempts were made to fit the experimental data with the Freundlich, Langmuir and Dubinin-Radushkevich isotherms. The R² values, which ranged from 0.8974-0.9898, 0.8848-0.9824 and 0.6235-0.9101 for Freundlich, Langmuir and Dubinin-Radushkevich isotherms respectively, showed that Freundlich isotherm gave a better fit followed by Langmuir and then Dubinin-Radushkevich isotherm. The sorption trend could be put as BOD > Colour > TSS. The apparent energy of adsorption was found to be 1.25, 0.58 and 0.97 (KJ/mol) for BOD, colour and TSS respectively, showing that sorption process occurs by physiosorption. Therefore, boiler fly ash is capable of reducing BOD, Colour and TSS from POME and hence could be used to develop a good adsorbent for POME treatment.

Prevalence of Lettuce mosaic virus - common strain on three lettuce producing areas from São Paulo State

LMV is one of the most important pathogens of lettuce worldwide. Based on their ability to overcome the resistance genes mo1¹ and mo1² in lettuce, isolates can be divided in two types: LMV-Most, which can infect and are seed-borne in cultivars containing the mo1 gene and LMV-Common, which do not cause symptoms on these cultivars and are seed transmitted only in susceptible cultivars. To evaluate the occurrence of these two types of LMV isolates, a survey was carried out during 2002-2005 in three lettuce production areas from São Paulo State. Total RNA was used for the diagnosis of LMV isolates by RT-PCR using universal primers for the variable N-terminus of the capsid protein, in the 3' end of the genome. Positives samples were analyzed by a second RT-PCR using specifics primers for LMV-Most isolates designed to amplify a fragment from the central region (CI-VPg) of the genome. A total of 1362 samples showing mosaic symptoms were collected and 504 (37.29 %) were positives for LMV. On susceptible lettuce cultivars, LMV-Common was prevalent (77.3%). LMV-Most was found frequently associated with tolerant (mo1¹) lettuce cultivars. Susceptible cultivars correspond today for most of the area of lettuce production. So, despite the ability of LMV-Most isolates to overcome the resistance provided by the recessive mo1¹ gene, they are not prevalent in the conditions of São Paulo State.

In vivo sensitivity reduction of Puccinia triticina races, causal agent of wheat leaf rust, to DMI and QoI fungicides

Experiments were carried out to determine in vivo the IC50 and the IC90 for demethylation-inhibitor fungicides (DMIs, triazoles) and quinone outside inhibitors (QoIs, strobilurins) to the five most frequent races of Puccinia triticina in 2007 growing season in Southern Brazil. The tests were done in a greenhouse with wheat seedlings. DMI fungicides were tested at the concentrations, in mg/L, 0.0; 0.02; 0.2; 2.0; 20.0; 100.0 and 200.0, and QoIs at the concentrations 0.0; 0.0001; 0.001; 0.01; 0.1; 1 and 10.0 mg of active ingredient/L water. Fungicides were preventively applied at 24 hours before the inoculation of seedlings with the fungal spores. The effect of treatments was assessed based on the number of uredia/cm². The lowest IC50 (inhibitory concentration) for DMI fungicides determined for MCG-MN, sensitive race, ranged from 0.33 to 0.91 mg/L, while the highest values for MDP-MR, MDT-MR, MDK-MR, MFH-HT races, varied from 9.63 to 85.64 mg/L (suspected insensitivity). QoI fungicide presented an IC50 varying from 0.0018 to 0.14 mg/L. The sensitivity reduction factor for DMIs varied from 8.8 to 238.8, and for QoIs from 0.3 to 1.5 mg/L. Sensitivity reduction was confirmed for the races MDP-MR, MDT-MR, MDK-MR, MFH-HT to DMIs, as well as their sensitivity to QoI fungicides.

Sensitivity reduction in Blumeria graminis f. sp. hordei to triadimenol fungicide applied as barley seed treatment

Experiments were carried out in a growth chamber with controlled temperature and photoperiod to test two populations of Blumeria graminis f. sp. hordei from Guarapuava, Paraná State, and Passo Fundo, Rio Grande do Sul State, Brazil. Treatments consisted in application of the fungicide triadimenol (Baytan 150 SC®) at three rates of its commercial formulation: 150, 250, 350 mL/100 Kg barley seeds. The experiments were conducted separately in a growth chamber for each population, adopting the same temperature and photoperiod. For inoculation, pots containing barley seedlings colonized by the fungus were placed among the plots. After emergence of the first symptoms, the disease severity was assessed at two-day intervals. The experiments were repeated twice for each fungus population. Data were expressed as area under the disease progress curve and as powdery mildew control by comparing the severity after the fungicide treatments to that of control. Data were subjected to analysis of variance and regression analysis; the area under the disease progress curve was also calculated. Comparing the data obtained in the present study with those reported in the literature and the control, the maximum value of 26.1% is considered insufficient to prevent the damages caused by the disease. The control response to the fungicide rate was significant. We can conclude that there was a reduction in the sensitivity of both B. graminis f.sp. hordei populations to the fungicide triadimenol, which explains the control failure observed in barley farms.

In vitro sensitivity reduction of Fusarium graminearum to DMI and QoI fungicides

In Brazil, Fusarium head blight (FHB) affecting wheat can cause up to 39.8% damage. Resistant cultivars are not available yet; thus, short-term disease control relies on the use of fungicides. The first step to improve control is to monitor fungal populations that are sensitivity to chemicals in order to achieve efficient FHB management. In vitro experiments were conducted to evaluate the inhibitory concentration (IC50) of fungicides for both mycelial growth and conidial germination of ten Fusarium graminearum isolates. The following demethylation inhibitor (DMI) fungicides were tested: metconazole, prothioconazole and tebuconazole. In addition, pyraclostrobin and trifloxystrobin were included, representing QoI fungicides, as well as three co-formulations containing metconazole + pyraclostrobin, prothioconazole + trifloxystrobin, and tebuconazole + trifloxystrobin. For mycelial growth, the overall mean IC50 of isolates was: metconazole 0.07, prothioconazole 0.1, and tebuconazole 0.19 mg/L. For the co-formulations, it was: prothioconazole + trifloxystrobin 0.08, tebuconazole + trifloxystrobin 0.12, and metconazole + pyraclostrobin 0.14 mg/L. Regarding spore germination inhibition, IC50 for prothioconazole + trifloxystrobin was 0.06, for tebuconazole + trifloxystrobin, 0.12 mg/L, for QoI alone pyraclostrobin, was 0.09, and for trifloxystrobin, 0.28 mg/L. There was a sensitivity shift among isolates and the highest fungitoxicity to F. graminearum was confirmed for prothioconazole, metconazole and tebuconazole .

In vivo sensitivity of Phakopsora pachyrhizi to DMI and QoI fungicides

In in vivoexperiments the sensitivity of 18 isolates of Phakopsora pachyrhizifrom several regions of Brazil to IDM fungicides (cyproconazole, epoxiconazole and tebuconazole and an IQE (pyraclostrobin) were evaluated. The assessments were based on leaflet uredia density. Inhibitory concentration (IC50) and sensitivity reduction factor were determined for all fungicide x strain interactions. Tebuconazole sensitivity reduction was detected for most fungus isolates. In contrast, there was no fungicide shift in sensitivity of the fungus to pyraclostrobin. We conclude that the control failure of soybean rust found in some farms is due to the reduced sensitivity of the fungus to the IDM fungicide and that it remains sensitive to pyraclostrobin.

Kaksoislaatuisesta rakenneputkesta hitsatun X-liitoksen kestävyys ja muodonmuutoskyky

Rautaruukki Oyj:n uusi Ruukki double grade S420MH/S355J2H -rakenneputki yhdistää putkilajien S420MH ja S355J2H ominaisuudet. Eurocode 3:n suunnitteluohjeiden mukaan Ruukki double graden käyttöön on sovellettava lujuusluokan S420 mukaista hitsien mitoitusta ja rakenneputkiliitosten staattista mitoituskestävyyttä alentavaa varmuuskerrointa, kun halutaan hyödyntää lujuusluokan S420 ominaisuudet Ruukki double gradea käytettäessä. Tässä työssä tutkittiin S420-lujuusluokkaa vastaavien suunnittelumääräysten soveltamistarvetta Ruukki double grade -rakenneputken käyttöön. Työn tavoitteena oli arvioida Ruukki double grade -rakenneputkesta hitsaamalla valmistetun X-liitoksen kestävyyden ja muodonmuutoskyvyn riittävyys, kun hitsit mitoitettiin S355-lujuusluokkaa vastaavien Eurocode 3:n suunnitteluohjeiden mukaisesti. X-liitosten kestävyyttä ja muodonmuutoskykyä tutkittiin kokeellisesti -40 C lämpötilassa suoritettujen laboratoriokokeiden avulla sekä analyyttisen laskennan ja elementtimenetelmän keinoin. Kestävyyden riittävyyttä arvioitiin vertaamalla laboratoriokokeista saatuja liitosten kestävyyksiä Eurocode 3:n ja myötöviivateorian mukaisiin kestävyyksiin. Elementtimenetelmän ja laboratoriokokeen pohjalta piirrettyjä liitoksen voima-siirtymäkuvaajia vertailtiin keskenään, kun elementtimalli analysoitiin eri materiaalimalleilla. Lisäksi verrattiin elementtimallin voima-venymäkuvaajia liitoksen venymäliuskan arvoihin. Kaikki koesarjan S355-lujuusluokan mukaisilla hitsin a-mitoilla valmistetut liitokset täyttivät kestävyydelle ja muodonmuutoskyvylle asetetut vaatimukset. Täten tämän koesarjan perusteella ei ollut tarpeellista soveltaa S420-lujuusluokan mukaista hitsien mitoitusta ja staattista mitoituskestävyyttä alentavaa varmuuslukua Ruukki double grade -rakenneputkeen. Elementtimenetelmästä ja laboratoriokokeesta saadut liitoksen voima-siirtymäkuvaajat vastasivat hyvin toisiaan. Sen sijaan elementtimallin voima-venymä-kuvaajat eivät vastanneet venymäliuskojen mittausdataa kovin hyvin.

Delay reduction in courts of justice – possibilities and challenges of process improvement in professional public organizations

Delays in the justice system have been undermining the functioning and performance of the court system all over the world for decades. Despite the widespread concern about delays, the solutions have not kept up with the growth of the problem. The delay problem existing in the justice courts processes is a good example of the growing need and pressure in professional public organizations to start improving their business process performance.This study analyses the possibilities and challenges of process improvement in professional public organizations. The study is based on experiences gained in two longitudinal action research improvement projects conducted in two separate Finnish law instances; in the Helsinki Court of Appeal and in the Insurance Court. The thesis has two objectives. First objective is to study what kinds of factors in court system operations cause delays and unmanageable backlogs and how to reduce and prevent delays. Based on the lessons learned from the case projects the objective is to give new insights on the critical factors of process improvement conducted in professional public organizations. Four main areas and factors behind the delay problem is identified: 1) goal setting and performance measurement practices, 2) the process control system, 3) production and capacity planning procedures, and 4) process roles and responsibilities. The appropriate improvement solutions include tools to enhance project planning and scheduling and monitoring the agreed time-frames for different phases of the handling process and pending inventory. The study introduces the identified critical factors in different phases of process improvement work carried out in professional public organizations, the ways the critical factors can be incorporated to the different stages of the projects, and discusses the role of external facilitator in assisting process improvement work and in enhancing ownership towards the solutions and improvement. The study highlights the need to concentrate on the critical factors aiming to get the employees to challenge their existing ways of conducting work, analyze their own processes, and create procedures for diffusing the process improvement culture instead of merely concentrating of finding tools, techniques, and solutions appropriate for applications from the manufacturing sector

Reduction of specific energy consumption of a thermomechanical pulping plant

Kuumahiertoprosessi on erittäin energiaintensiivinen prosessi, jonka energianominaiskulutus (EOK) on yleisesti 2–3.5 MWh/bdt. Noin 93 % energiasta kuluu jauhatuksessa jakautuen niin, että kaksi kolmasosaa kuluu päälinjan ja yksi kolmasosa rejektijauhatuksessa. Siksi myös tämän työn tavoite asetettiin vähentämään energian kulutusta juuri pää- ja rejektijauhatuksessa. Päälinjan jauhatuksessa tutkimuskohteiksi valittiin terityksen, tehojaon ja tuotantotason vaikutus EOK:een. Rejektijauhatuksen tehostamiseen pyrittiin yrittämällä vähentää rejektivirtaamaa painelajittelun keinoin. Koska TMP3 laitoksen jauhatuskapasiteettia on nostettu 25 %, tavoite oli nostaa päälinjan lajittelun kapasiteettia saman verran. Toisena tavoitteena oli pienentää rejektisuhdetta pää- ja rejektilajittelussa ja siten vähentää energiankulutusta rejektijauhatuksessa. Näitä tavoitteita lähestyttiin vaihtamalla päälinjan lajittimiin TamScreen-roottorit ja rejektilajittimiin Metso ProFoil-roottorit ja optimoimalla kuitufraktiot sihtirumpu- ja prosessiparametrimuutoksin. Syöttävällä terätyypillä pystyttiin vähentämään EOK:ta 100 kWh/bdt, mutta korkeampi jauhatusintensiteetti johti myös alempiin lujuusominaisuuksiin, korkeampaan ilmanläpäisyyn ja korkeampaan opasiteettiin. Myös tehojaolla voitiin vaikuttaa EOK:een. Kun ensimmäisen vaiheen jauhinta kuormitettiin enemmän, saavutettiin korkeimmillaan 70 kWh/bdt EOK-vähennys. Tuotantotason mittaamisongelmat heikensivät tuotantotasokoeajojen tuloksia siinä määrin, että näiden tulosten perusteella ei voida päätellä, onko EOK tuotantotasoriippuvainen vai ei. Päälinjan lajittelun kapasiteettia pystyttiin nostamaan TS-roottorilla vain 18 % jääden hieman tavoitetasosta. Rejektilajittelussa pystyttiin vähentämään rejektimäärää huomattavasti Metso ProFoil-roottorilla sekä sihtirumpu- ja prosessiparametrimuutoksin. Lajittamokehityksellä saavutettu EOK-vähennys arvioitiin massarejektisuhteen pienentymisen ja rejektijauhatuksessa käytetyn EOK:n avulla olevan noin 130 kWh/bdt. Yhteenvetona voidaan todeta, että tavoite 300 kWh/bdt EOK-vähennyksestä voidaan saavuttaa työssä käytetyillä tavoilla, mikäli niiden täysi potentiaali hyödynnetään tuotannossa.

Raw water use charge reduction for the rural sector in the PCJ Watershed

The deficient environmental preservation on agricultural properties has reflected in great soil losses for erosion and the high rate of sedimentation. Therefore, this work brings the application of software to demonstrate that planters can get benefits by the conservationist practices. The benefits will be obtained from the environment aspect (erosion and sedimentation control), as well as economical aspect (financial incentives). A proposal has been created by the Technical Chamber of Rural Water Use and Conservation (CT-Rural) to estimate the reduction in raw water use charge for the rural water users of the PCJ Watershed - this reduction is being possible since January 2007, at the PCJ Committee. The software develops a simple relationship, so that if the rural conservationist action goes more efficient, such as if the conserved rural area goes larger, then the reduction value will bring better benefits for the rural water users. Within the purposes of this study, there is the idealization of mechanisms that may support specific management matters related to the water users of federal rivers from the rural sector of PCJ Watershed.

Relative reduction in annual soil loss in micro watersheds due to the relief and forest cover

With the intense debate, in Brazil, between landowners and public agencies about the amount of area with forest cover needed in different regions, there is an increase of the need for provision of technical data used as a basis for decision making. One of the criteria to evaluate the effect of forest cover in protecting water resources is the soil loss, which leads to several consequences on the environment, including the silting of the rivers. Therefore, this study aimed to evaluate the reduction in the soil loss in micro watersheds with different reliefs, size and location of forest cover, in the Corumbataí River watershed, in the state of São Paulo, using the Revised Universal Soil Loss Equation (RUSLE) in a GIS environment. For this study, 18 watersheds in three degrees of slope were selected, and 20 scenarios for land-use were established, by analyzing the influence of the PPA size, and the size and the location of the Legal Reserve. The results showed that: a) the effect of forest cover in reducing annual soil loss varies depending on the average slope of the watershed; b) the PPA width must be determined taking into account the slope of the watershed; c) the Legal Reserve must be located along the PPA. These provide better results in reducing annual soil loss.