Summer ozone cycles in the Lisbon metropolitan area and its relation to some meteorological variables

The aim of this work is to study the tropospheric ozone concentrations and daily peak cycles in the Lisbon MetropolitanArea (LMA) during the summer season (June, July and August, JJA) covering the 4-yr study period 2002-2005. Theresults show that all the stations have the same pattern: a minimum in the early morning followed by an increase at 1000UTC reaching to a peak at 1300-1400 UTC, dropped again to minimum values 1800 UTC but with different concentrationsdue to regional and local wind circulations and complex dynamic interactions. We identified in Lisbon city the ozone “weekendeffect”. Finally, we studied an episode of very high levels of tropospheric ozone and related daily ozone concentrationswith some meteorological variables.

TCF-valkaisimon laatuvaihtelun pienentäminen

Tämän diplomityön tavoitteena oli pienentää TCF-valkaisimon laatuvaihtelua ja vähentää kemikaaleista aiheutuvia kustannuksia. Työn kirjallisuusosassa tarkasteltiin valkaisuun vaikuttavia tekijöitä. Valkaisukemikaaleista olivat mukana TCF-valkaisussa käytettävät otsoni ja vetyperoksidi. Lisäksi selvitettiin metallien poistoa massasta sekä vesikierron sulkemisesta aiheutuvia ongelmia. Kokeellisessa osassa etsittiin Oy Metsä-Botnia Ab Rauman tehtaan valkaisuprosessin suurimmat laatuominaisuuksien vaihteluun vaikuttavat tekijät. Tavoitteena oli pienentää vaihtelua valmiin massan laatuominaisuuksissa sekä vähentää raaka-aineista ja kemikaaleista aiheutuvia kustannuksia laatuominaisuuksien tasoa laskematta. Tutkimuksessa käytettiin hyväksi Taguchi-menetelmää sekä monimuuttuja-analyysiä. Tutkimuksessa tehtiin kaksi Taguchi-koetta, joissa tutkittiin valkaisimon ensimmäistä otsonivaihetta sekä koko valkaisimoa. Otsonivaiheen merkittävimmiksi tekijöiksi osoittautuivat otsoniannos, otsonin väkevyys sekä pH. Kaikkia valkaisimon vaiheita tutkittaessa löydettiin merkittävimmiksi tekijöiksi ensimmäisen peroksidivaiheen lämpötila, vetyperoksidin jakaminen peroksidivaiheisiin, kelatointi sekä otsonivaiheen otsoniannos ja pH. Optimiajomallin avulla saatiin valkaisimon laatuvaihtelua pienennettyä. Kemikaalikustannuksiin vaikuttavista tekijöistä merkittävimmiksi osoittautuivat kelatoinnin vaikutus, vetyperoksidin annosteleminen molempiin vaiheisiin sekä ensimmäisen peroksidivaiheen lämpötila. Optimiajomallien avulla vetyperoksidikulutusta saatiin pienennettyä noin 24 %.

Evidence for the influence of the North Atlantic Oscillation on the total ozone column at northern low latitudes and midlatitudes during winter and summer seasons.

The strong influence of the winter North Atlantic Oscillation (NAO) on the total ozone column (TOC) in the Northern Hemisphere has been reported in a number of previous studies. In this study we show that this influence is not restricted to the winter season but is also significant in summer. Especially interesting effects of the summer NAO (SNAO) on the TOC are observed over the eastern Mediterranean region, where a strongly positive SNAO index is related to the creation of a geopotential height-negative anomaly over Greece with maximum amplitude at 200 hPa. Another anomaly was observed west of the Iberian Peninsula with similar effects on the TOC. Analyzing 26 years of Total Ozone Mapping Spectrometer (TOMS) and Ozone Monitoring Instrument (OMI) data from the equator to midlatitudes (60°) in the Northern Hemisphere, we demonstrate that the SNAO accounts for up to 30% of the TOC variability with a strong latitudinal and longitudinal dependence. Additionally, we obtain significant correlations between the NAO index and the thermal tropopause pressure and also with the geopotential heights at 200 and 500 hPa. Finally, some indirect connections between NAO and the TOC through teleconnections are also discussed.

APPLICATION OF OZONE AIMING TO KEEP THE QUALITY OF STRAWBERRIES USING A LOW COST REACTOR

RESUMO O morango é uma fruta de alto valor comercial e tem uma rápida deterioração, como a demanda por produtos saudáveis, seguros sob o ponto de vista microbiológico e livre de produtos químicos aumenta cada vez mais, o método de aplicação do gás ozônio em uma atmosfera controlada foi proposto. O objetivo deste trabalho foi verificar a eficiência do gás ozônio produzido por um reator, a fim de que os pequenos produtores de morangos possam usá-lo, contribuindo, assim, para as economias regionais. Morangos (Fragaria ananassa) variedade Oso Grande, colhidasna região de Minas Gerais foram divididas dois grupos: o primeiro recebeu tratamento com ozônio e o segundo não. No primeiro grupo, o ozônio foi aplicado durante 20 minutos a partir de um reator de Corona. Os frutos foram armazenados a 4 ° C, por períodos de 5, 10 e 15 dias. A qualidade dos frutos foi relata a partir dos níveis de sólidos solúveis totais (SS), acidez titulável (AT ), pH, compostos fenólicos (CF), ácido ascórbico (AA), perda de massa fresca (PM%) e análise microbiológica (AM), em diferentes tempos de armazenamento de frutos ozonizados e não ozonizados. O uso de gás ozônio foi eficiente para a pós-colheita de morango. Os níveis de microrganismos estão dentro dos limites aceitáveis e as propriedades físicas e químicas foram mantidas.

Evaluating the Performance of a Regional-Scale Photochemical Modelling System: Part I Ozone Predictions

We present a detailed evaluation of the seasonal performance of the Community Multiscale Air Quality (CMAQ) modelling system and the PSU/NCAR meteorological model coupled to a new Numerical Emission Model for Air Quality (MNEQA). The combined system simulates air quality at a fine resolution (3 km as horizontal resolution and 1 h as temporal resolution) in north-eastern Spain, where problems of ozone pollution are frequent. An extensive database compiled over two periods, from May to September 2009 and 2010, is used to evaluate meteorological simulations and chemical outputs. Our results indicate that the model accurately reproduces hourly and 1-h and 8-h maximum ozone surface concentrations measured at the air quality stations, as statistical values fall within the EPA and EU recommendations. However, to further improve forecast accuracy, three simple bias-adjustment techniques mean subtraction (MS), ratio adjustment (RA), and hybrid forecast (HF) based on 10 days of available comparisons are applied. The results show that the MS technique performed better than RA or HF, although all the bias-adjustment techniques significantly reduce the systematic errors in ozone forecasts.

Electrochemistry and green chemical processes: electrochemical ozone production

After an introductory discussion emphasising the importance of electrochemistry for the so-called Green Chemical Processes, the article presents a short discussion of the classical ozone generation technologies. Next a revision of the electrochemical ozone production technology focusing on such aspects as: fundamentals, latest advances, advantages and limitations of this technology is presented. Recent results about fundamentals of electrochemical ozone production obtained in our laboratory, using different electrode materials (e.g. boron doped diamond electrodes, lead dioxide and DSAÒ-based electrodes) also are presented. Different chemical processes of interest to the solution of environmental problems involving ozone are discussed.

Trends and strategies of ozone application in environmental problems

Efforts presented by the scientific community in recent years towards the development of numerous green chemical processes and wastewater treatment technologies are presented and discussed. In the light of these approaches, environmentally friendly technologies, as well as the key role played by the well-known advanced oxidation processes, are discussed, giving special attention to the ones comprising ozone applications. Fundamentals and applied aspects dealing with ozone technology and its application are also presented.

Influence of EfOM on the oxidation of micropollutants by Ozone and UV/H2O2 in secondary effluents

The aim of this work was to study the influence of effluent organic matter (EfOM) on micropollutants removal by ozone and UV/H2O2. To perform the experiments, deionized water and municipal secondary effluents (SE) were artificially contaminated with atrazine (ATZ) and treated by the two proposed methods. ATZ concentration, COD and TOC were recorded along the reaction time and used to evaluate EfOM effect on the system efficiency. Results demonstrate that the presence of EfOM can significantly reduce the micropollutant removal rate due to competition of EfOM components to react with radicals and/or molecular ozone. The hydroxyl radical scavenging caused by EfOM was quantified as well as the contribution of molecular ozone and �OH radicals during the ozonation of SE. EfOM components promoted higher inhibition of ATZ oxidation by hydroxyl radicals than by molecular ozone.

Water circulations for effective bleaching of high-brightness mechanical pulps

The amount of water available is usually restricted, which leads to a situation where a complete understanding of the process, including water circulations and the influence of water components, is essential. The main aim of this thesis was to clarify the possibilities for the efficient use of residual peroxide by means of water circulation rearrangements. Rearranging water circulations and the reduction of water usage may cause new problems, such as metal induced peroxide decomposition that needs to be addressed. This thesis introduces theoretical methods of water circulations to combine two variables; effective utilization of residual peroxide and avoiding manganese in the alkaline peroxide bleaching stage. Results are mainly based on laboratory and mill site experiments concerning the utilization of residual peroxide. A simulation model (BALAS) was used to evaluate the manganese contents and residual peroxide doses. It was shown that with optimum recirculation of residual peroxide the brightness can be improved or chemical costs can be decreased. From the scientific perspective, it was also very important to discover that recycled peroxide was more effective pre-bleaching agent compared to fresh peroxide. This can be due to the organic acids i.e. per acetic acid in wash press filtrate that have been formed in alkaline bleaching stage. Even short retention time was adequate and the activation of residual peroxide using sodium hydroxide was not necessary. There are several possibilities for using residual peroxide in practice regarding bleaching. A typical modern mechanical pulping process line consist of defibering, screening, a disc filter, a bleach press, high consistency (HC) peroxide bleaching and a wash press. Furthermore there usually is not a particular medium consistency (MC) pre-bleaching stage that includes additional thickening equipment. The most advisable way to utilize residual peroxide in this kind of process is to recycle the wash press filtrate to the dilution of disc filter pulp (low MC pre-bleaching stage). An arrangement such as this would be beneficial in terms of the reduced convection of manganese to the alkaline bleaching stage. Manganese originates from wood material and will be removed to the water phase already in the early stages of the process. Recycling residual peroxide prior to the disc filter is not recommended because of low consistencies. Regarding water circulations, the novel point of view is that, it would be beneficial to divide water circulations into two sections and the critical location for the division is the disc filter. Both of these two sections have their own priority. Section one before the disc filter: manganese removal. Section two after the disc filter: brightening of pulp. This division can be carried out if the disc filter pulp is diluted only by wash press filtrate before the MC storage tower. The situation is even better if there is an additional press after the disc filter, which will improve the consistency of the pulp. This has a significant effect on the peroxide concentration in the MC pre-bleaching stage. In terms of manganese content, it is essential to avoid the use of disc filter filtrate in the bleach press and wash press showers. An additional cut-off press would also be beneficial for manganese removal. As a combination of higher initial brightness and lower manganese content, the typical brightness increase varies between approximately 0.5 and 1% ISO units after the alkaline peroxide bleaching stage. This improvement does not seem to be remarkable, but as it is generally known, the final brightness unit is the most expensive and difficult to achieve. The estimation of cost savings is not unambiguous. For example in GW/TMP mill case 0.6% ISO units higher final brightness gave 10% savings in the costs of bleaching chemicals. With an hypothetical 200 000 ton annual production, this means that the mill could save in the costs of bleaching chemicals more than 400 000 euros per year. In general, it can be said that there were no differences between the behavior of different types of processes (GW, PGW, TMP and BCTMP). The enhancement of recycling gave a similar response in all cases. However, we have to remember that the utilization of residual peroxide in older mills depends a great deal on the process equipment, the amount of water available and existing pipeline connections. In summary, it can be said that processes are individual and the same solutions cannot be applied to all cases.

The effect of pulp washing on bleaching efficiency

The main aim of this study was to inspect the influence of the ultrafiltration implementation on the washing and on bleaching efficiency. Four cases corresponding to four washing stages were observed: two with hardwood pulp and two with softwood pulp; each case had a reference and a trial experiment. The experiments with hardwood pulp were arranged in a manner to explore predominantly the possibility of bleaching performance improvement by applying for washing instead of untreated filtrate (reference case) the same treated one (trial case). Despite that the ultrafiltration reduced the COD of the wash filtrates allowing the decreasing of COD carry-over to the bleaching stage it didn’t affect the bleaching performance. Another set was used in the experiments with softwood pulp. It implied the ultrafiltration and recirculation of the filtrate to the same washing stage with the purpose to reduce the volumes and pollution of the bleaching effluents. In one case the negative result was obtained which was expressed by worse parameters of the pulp after bleaching. Another case showed the opportunity to replace hot water with the filtrate and reduce the fresh water consumption.

Final chlorine dioxide stage at near-neutral pH for bleaching eucalypt pulp

It is well known that pH is an important parameter for controlling the eucalyptus pulp bleaching when using the final chlorine dioxide stage, since it affects the effectiveness of the process. Recommendations found in the literature for operating are in the 3.5 to 4.0 range. However, in this paper it was shown that final chlorine dioxide has better performance, with significant brightness gain while also preserving pulp quality, when it is operated at near neutral pH. This result can be explained by the generation of sodium bicarbonate in situ upon adding carbon dioxide at this stage.

The effect of wood supply and bleaching process on pulp brightness stability

One hundred different 5.5-year-old Eucalyptus grandis x Eucalyptus urophylla wood clones were cooked to kappa number 15-17.5 and the resulting kraft pulps oxygen-delignified to kappa 9.5-11.5 under fixed conditions, except for chemical charges. Thirteen samples showing large variations in effective alkali requirement, pulp yield and O-stage efficiency and selectivity were selected for brightness reversion studies. These samples were bleached to 90-91% ISO by DEDD and DEDP sequences and their brightness stability and chemical characteristics determined. Heat reversion of the eucalyptus kraft pulps was strongly influenced by the wood supply, with brightness loss varying in the range of 2.1-3.6 and 0.8-1.7 %ISO for ODEDD and ODEDP bleached pulps, respectively. Pulps bleached by the ODEDP sequence showed reversion values 1.3-1.9 % ISO lower than those bleached by the ODEDD sequence. Pulp carbonyl content decreased by 35-40% during the final peroxide bleaching stage. Carbonyl and carboxyl groups correlated positively with brightness reversion, as did permanganate number and acid soluble lignin. Pulp final viscosity and metal and DCM extractives contents showed no significant correlation with brightness reversion. Pulping, oxygen delignification and ECF bleaching performances also showed no correlation with brightness reversion.