Wet Oxidation of Concentrated Wastewaters: Process Combination and Reaction Kinetic Modeling

The accumulation of aqueous pollutants is becoming a global problem. The search for suitable methods and/or combinations of water treatment processes is a task that can slow down and stop the process of water pollution. In this work, the method of wet oxidation was considered as an appropriate technique for the elimination of the impurities present in paper mill process waters. It has been shown that, when combined with traditional wastewater treatment processes, wet oxidation offers many advantages. The combination of coagulation and wet oxidation offers a new opportunity for the improvement of the quality of wastewater designated for discharge or recycling. First of all, the utilization of coagulated sludge via wet oxidation provides a conditioning process for the sludge, i.e. dewatering, which is rather difficult to carry out with untreated waste. Secondly, Fe2(SO4)3, which is employed earlier as a coagulant, transforms the conventional wet oxidation process into a catalytic one. The use of coagulation as the post-treatment for wet oxidation can offer the possibility of the brown hue that usually accompanies the partial oxidation to be reduced. As a result, the supernatant is less colored and also contains a rather low amount of Fe ions to beconsidered for recycling inside mills. The thickened part that consists of metal ions is then recycled back to the wet oxidation system. It was also observed that wet oxidation is favorable for the degradation of pitch substances (LWEs) and lignin that are present in the process waters of paper mills. Rather low operating temperatures are needed for wet oxidation in order to destruct LWEs. The oxidation in the alkaline media provides not only the faster elimination of pitch and lignin but also significantly improves the biodegradable characteristics of wastewater that contains lignin and pitch substances. During the course of the kinetic studies, a model, which can predict the enhancements of the biodegradability of wastewater, was elaborated. The model includes lumped concentrations suchas the chemical oxygen demand and biochemical oxygen demand and reflects a generalized reaction network of oxidative transformations. Later developments incorporated a new lump, the immediately available biochemical oxygen demand, which increased the fidelity of the predictions made by the model. Since changes in biodegradability occur simultaneously with the destruction of LWEs, an attempt was made to combine these two facts for modeling purposes.

Active sulphide mine tailings impoundments as sources of contaminated drainage: controlling factors, methods of characterisation and geochemical constraints for mitigation

Low quality mine drainage from tailings facilities persists as one of the most significant global environmental concerns related to sulphide mining. Due to the large variation in geological and environmental conditions at mine sites, universal approaches to the management of mine drainage are not always applicable. Instead, site-specific knowledge of the geochemical behaviour of waste materials is required for the design and closure of the facilities. In this thesis, tailings-derived water contamination and factors causing the pollution were investigated in two coeval active sulphide mine sites in Finland: the Hitura Ni mine and the Luikonlahti Cu-Zn-Co-Ni mine and talc processing plant. A hydrogeochemical study was performed to characterise the tailingsderived water pollution at Hitura. Geochemical changes in the Hitura tailings were evaluated with a detailed mineralogical and geochemical investigation (solid-phase speciation, acid mine drainage potential, pore water chemistry) and using a spatial assessment to identify the mechanisms of water contamination. A similar spatial investigation, applying selective extractions, was carried out in the Luikonlahti tailings area for comparative purposes (Hitura low-sulphide tailings vs. Luikonlahti sulphide-rich tailings). At both sites, hydrogeochemistry of tailings seepage waters was further characterised to examine the net results of the processes observed within the impoundments and to identify constraints for water treatment. At Luikonlahti, annual and seasonal variation in effluent quality was evaluated based on a four-year monitoring period. Observations pertinent to future assessment and mine drainage prevention from existing and future tailings facilities were presented based on the results. A combination of hydrogeochemical approaches provided a means to delineate the tailings-derived neutral mine drainage at Hitura. Tailings effluents with elevated Ni, SO₄ ^2- and Fe content had dispersed to the surrounding aquifer through a levelled-out esker and underneath the seepage collection ditches. In future mines, this could be avoided with additional basal liners in tailings impoundments where the permeability of the underlying Quaternary deposits is inadequate, and with sufficiently deep ditches. Based on the studies, extensive sulphide oxidation with subsequent metal release may already initiate during active tailings disposal. The intensity and onset of oxidation depended on e.g. the Fe sulphide content of the tailings, water saturation level, and time of exposure of fresh sulphide grains. Continuous disposal decreased sulphide weathering in the surface of low-sulphide tailings, but oxidation initiated if they were left uncovered after disposal ceased. In the sulphide-rich tailings, delayed burial of the unsaturated tailings had resulted in thick oxidized layers, despite the continuous operation. Sulphide weathering and contaminant release occurred also in the border zones. Based on the results, the prevention of sulphide oxidation should already be considered in the planning of tailings disposal, taking into account the border zones. Moreover, even lowsulphide tailings should be covered without delay after active disposal ceases. The quality of tailings effluents showed wide variation within a single impoundment and between the two different types of tailings facilities assessed. The affecting factors included source materials, the intensity of weathering of tailings and embankment materials along the seepage flow path, inputs from the process waters, the water retention time in tailings, and climatic seasonality. In addition, modifications to the tailings impoundment may markedly change the effluent quality. The wide variation in the tailings effluent quality poses challenges for treatment design. The final decision on water management requires quantification of the spatial and seasonal fluctuation at the site, taking into account changes resulting from the eventual closure of the impoundment. Overall, comprehensive hydrogeochemical mapping was deemed essential in the identification of critical contaminants and their sources at mine sites. Mineralogical analysis, selective extractions, and pore water analysis were a good combination of methods for studying the weathering of tailings and in evaluating metal mobility from the facilities. Selective extractions with visual observations and pH measurements of tailings solids were, nevertheless, adequate in describing the spatial distribution of sulphide oxidation in tailings impoundments. Seepage water chemistry provided additional data on geochemical processes in tailings and was necessary for defining constraints for water treatment.

Kohti vesiensuojelun aikaa; veden laadun muutokset eteläisimmällä Saimaalla

Työn tarkoituksena on ollut tutkia vesianalytiikan kehitystä Suomessa, arvioida rutiini-analytiikan luotettavuutta, selvittää eteläisimmän Saimaan jätevesikuormituksen kehitys ja siihen vaikuttaneet tekijät, laatia aikasarjat eräiden tutkimusalueen keskeisten veden laadun seurantapaikkojen veden laadun kehityksestä ja esittää keinoja veden laadun kehityksen kuvaa¬miseksi tiivistämällä suuri havaintomateriaali yksinkertaisiksi tunnusluvuiksi. Työssä käsiteltä¬vä aikajakso alkaa 1900-luvun alusta ja päättyy vuoteen 1998. Tutkimus on osa laajempaa ko¬konaisuutta. Tutkimusalue käsittää Vuoksen vesistön keskusjärven, Saimaan, eteläisimmät osat eli Pien-Saimaan, Suur-Saimaan, Vuoksen niskan ja Haapaveden altaat sekä vesistön purku¬-uoman, Vuoksen virran (ks. kuvat 5.1. ja 5.2.). Veden laatu alueen luonnontilaisilla alueilla on luokiteltavissa osin oligotrofiseksi, osin lievästi dysoligotrofiseksi. Sadan viimeisen vuoden aikana teollinen toiminta on muuttanut sitä voimakkaasti. Vesiensuojeluun on eteläisimmän Saimaan alueella investoitu yli 1,5 miljardia markka viimeisten noin 30 vuoden aikana. Investointien tuloksena kuormitus on laskenut oleellisesti 1960-luvun maksimikuormituksesta. Jätevesien purkuvesistön veden laatu on tänä aikana myös merkittävästi parantunut. Tämä on osoitettu veden laadun seurantatuloksista tehtyjen erilaisten tarkastelujen avulla (aikasarjadiagrammit, tilasto tarkastelut, indeksilukuluokitukset, PCA- ja PLS- ja DPLS- monimuuttujamallinnukset). Nykyisin veden laatu on lähes koko tutkimusalu¬eella vähintään tyydyttävä. Fysikaalis-kemiallisen veden laadun seurannan historia on Suomessa kansainvälisesti ja kansallisesti pitkä, ja Saimaalta voidaan veden laadun kehitystä arvioida luotettavasti 40 vuoden ajalta. Tutkimusmetodiikat vesitutkimusten pioneerimaissa ovat olleet samankaltaisia ja niiden perusteella on laadittu myös eurooppalaisen vedenlaadunseurannan suositukset. Vaikka tulevai¬suudessa vesistöä ja sen tilan kehitystä on tarkasteltava ekologisena kokonaisuutena, ei tätä voida tehdä ilman nykyisen kaltaista monitorointia. Teollisuuden jätevesikuormitus on laskenut neljännesvuosisadan aikana hyvin merkittä¬västi tavalla, joka vielä kymmenkunta vuotta sitten tuntui saavuttamattomalta. Saimaan. kuten muunkin Suomen metsäteollisuuden taso onkin kansainvälisesti korkea ja täyttää jo nyt kuormi¬tuksen suhteen lähes 2000-luvun alun BAT-tekniikan vaatimukset. Veden laatu ei kuitenkaan ole kuormitetuilla alueilla kaikkialla vielä hyvä, joten vesiensuojeluun on edelleen panostettava, kun tavoitteena on vesien hyvä ekologinen tila. Vesistöstä käsin tarkasteltuna hitaasti hajoavan orgaanisen aineen määrän vähentäminen vedestä on oltava seuraavana tavoitteena. Tätä tukee myös BAT-tekniikan tarkastelu.

Perceptions of green branding and identity building amongst small Finnish textile producers

The textile industry is one of the most polluting industries in the world. The amount of air and water pollution it causes puts a burden on the environment. There are companies who have taken the environmental and social aspects into account in the their production and chosen to operate in a green manner. This thesis studies how the phenomenon of green branding is seen from the perspectives of small Finnish textile companies. The theory used in this thesis has to do with green branding and identity building. The theory is used to analyze the results of the empirical findings. The main research question that the thesis aims to answer is how green branding is perceived within the Finnish textile industry. In order to answer the main research question, empirical data was collected from five relevant companies within the Finnish textile industry. The companies interviewed for the study were WST, Saana ja Olli, RCM, R-collection and Tiensivu. The study was conducted as a multiple case based study where multiple experts from green companies were interviewed. The experts were all owners or employees of companies that have a so-called green brand identity. The data was collected through semi-structured interviews, where the relevant experts from each company were interviewed either by themselves, in pairs or in groups. The data that was collected for this study was primary data, and the results of the study are mainly based on the experiences and opinions of the experts interviewed. The data collected does not cover the entire green textile industry within Finland, but study does however give a fairly comprehensive view of the phenomenon, as the textile industry in Finland is quite concise. The general findings of the study show that all experts from the companies interviewed agreed that a green brand identity does benefit their company in one way or the other. The findings also show contradictions with the older theory (eg. Charter et al. 1999, Pickett et al. 1995), and perhaps give a more modern view of the thoughts within the industry.

Pasvik Water Quality Report Environmental Monitoring Programme in the Norwegian, Finnish and Russian Border Area

The Pasvik monitoring programme was created in 2006 as a result of the trilateral cooperation, and with the intention of following changes in the environment under variable pollution levels. Water quality is one of the basic elements of the Programme when assessing the effects of the emissions from the Pechenganikel mining and metallurgical industry (Kola GMK). The Metallurgic Production Renovation Programme was implemented by OJSC Kola GMK to reduce emissions of sulphur and heavy metal concentrated dust. However, the expectations for the reduction in emissions from the smelter in the settlement Nikel were not realized. Nevertheless, Kola GMK has found that the modernization programme’s measures do not provide the planned reductions of sulfur dioxide emissions. In this report, temporal trends in water chemistry during 2000–2009 are examined on the basis of the data gathered from Lake Inari, River Pasvik and directly connected lakes, as well as from 26 small lakes in three areas: Pechenganikel (Russia), Jarfjord (Norway) and Vätsäri (Finland). The lower parts of the Pasvik watercourse are impacted by both atmospheric pollution and direct wastewater discharge from the Pechenganikel smelter and the settlement of Nikel. The upper section of the watercourse, and the small lakes and streams which are not directly linked to the Pasvik watercourse, only receive atmospheric pollution. The data obtained confirms the ongoing pollution of the river and water system. Copper (Cu), nickel (Ni) and sulphates are the main pollution components. The highest levels were observed close to the smelters. The most polluted water source of the basin is the River Kolosjoki, as it directly receives the sewage discharge from the smelters and the stream connecting the Lakes Salmijarvi and Kuetsjarvi. The concentrations of metals and sulphates in the River Pasvik are higher downstream from the Kuetsjarvi Lake. There has been no fall in the concentrations of pollutants in Pasvik watercourse over the last 10 years. Ongoing recovery from acidification has been evident in the small lakes of the Jarfjord and Vätsäri areas during the 2000s. The buffering capacity of these lakes has improved and the pH has increased. The reason for this recovery is that sulphate deposition has decreased, which is also evident in the water quality. However, concentrations of some metals, especially Ni and Cu, have risen during the 2000s. Ni concentrations have increased in all three areas, and Cu concentrations in the Pechenganickel and Jarfjord areas, which are located closer to the smelters. Emission levels of Ni and Cu did not fall during 2000s. In fact, the emission levels of Ni compounds even increased compared to the 1990s.

Pasvik Water Quality until 2013 ; Environmental Monitoring Programme in the Norwegian, Finnish and Russian Border Area

The Pasvik monitoring programme was created in 2006 as a result of the trilateral cooperation and with the intention of following changes in the environment under variable pollution levels. Water quality is one of the basic elements of the programme when assessing the effects of the emissions from the Pechenganikel mining end metallurgical industry (Kola GMK). In this report temporal trends of the water chemistry during 2000–2013 are examined on the basis of the data gathered from lake Inari, River Pasvik and directly connected lakes, Lake Kuetsjarvi and 25 small lakes in three areas: Pechenganikel (Russia), Jarfjord (Norway) and Vätsäri (Finland). The lower parts of the Pasvik watercourse are impacted by both atmospheric pollution and direct wastewater discharge from the Pechenganikel smelter and the settlement of Nikel. The upper section of the watercourse and the small lakes and streams which are not directly linked to the Pasvik Watercourse only receive atmospheric pollution. Lake Inari is free of direct emissions from the Pechenganikel and the water quality is excellent. In River Pasvik and the directly connected lakes copper, nickel, and sulphates are the main pollutants. The most polluted water body is the Kolosjoki River as well as the stream connecting the Lakes Salmijarvi and Kuetsjarvi. The concentration of metals and sulphates in the water notably increases downstream the river lower Lake Kuetsjarvi. In Lake Kuetsjarvi copper and nickel concentrations are clearly elevated and have changed insignificantly in the last years of the research period. In the small border area lakes recovery from acidification in Vätsäri and Jarfjord is evident. Nickel and copper oncentrations have fluctuated but remained on clearly elevated level in Jarfjord and Pechenga. Copper concentrations have been slightly rising in the recent years. In Pechenga area nickel concentrations during the last four monitoring years are decreasing in some places but the regional trend through whole time series is still positive.

Modification of Photocatalyst with Enhanced Photocatalytic Activity for Water

Increasing demand and shortage of energy resources and clean water due to the rapid development of industry, population growth and long term droughts have become an issue worldwide. As a result, global warming, long term droughts and pollution-related diseases are becoming more and more serious. The traditional technologies, such as precipitation, neutralization, sedimentation, filtration and waste immobilization, cannot prevent the pollution but restrict the waste chemicals only after the pollution emission. Meanwhile, most of these treatments cannot thoroughly degrade the contaminants and may generate toxic secondary pollutants into ecosystem. Heterogeneous photocatalysis as the innovative wastewater technology attracts many attention, because it is able to generate highly reactive transitory species for total degradation of organic compounds, water pathogens and disinfection by-products. Semiconductor as photocatalysts have demonstrated their efficiency in degrading a wide range of organics into readily biodegradable compounds, and eventually mineralized them to innocuous carbon dioxide and water. But, the efficiency of photocatalysis is limited, and hence, it is crucial issue to modify photocatalyst to enhance photocatalytic activity. In this thesis, first of all, two literature views are conducted. A survey of materials for photocatalysis has been carried out in order to summarize the properties and the applications of photocatalysts that have been developed in this field. Meanwhile, the strategy for the improvement of photocatalytic activity have been explicit discussed. Furthermore, all the raw material and chemicals used in this work have been listed as well as a specific experimental process and characterization method has been described. The synthesize methods of different photocatalysts have been depicted step by step. Among these cases, different modification strategies have been used to enhance the efficiency of photocatalyst on degradation of organic compounds (Methylene Blue or Phenol). For each case, photocatalytic experiments have been done to exhibit their photocatalytic activity.The photocatalytic experiments have been designed and its process have been explained and illustrated in detailed. Moreover, the experimental results have been shown and discussion. All the findings have been demonstrated in detail and discussed case by case. Eventually, the mechanisms on the improvement of photocatalytic activities have been clarified by characterization of samples and analysis of results. As a conclusion, the photocatalytic activities of selected semiconductors have been successfully enhanced via choosing appropriate strategy for the modification of photocatalysts.