abstract: The focus of this thesis is to study dissolved organic carbon composition and reactivity along the Colorado and Green Rivers. Dissolved organic carbon (DOC) in large-scale, managed rivers is relatively poorly studied as most literature has focused on pristine unmanaged rivers. The Colorado River System is the 7th largest in the North America; there are seventeen large dams along the Colorado and Green River. DOC in rivers and in the lakes formed by dams (reservoirs) undergo photo-chemical and bio-degradation. DOC concentration and composition in these systems were investigated using bulk concentration, optical properties, and fluorescence spectroscopy. The riverine DOC concentration decreased from upstream to downstream but there was no change in the specific ultraviolet absorbance at 254 nm (SUVA254). Total fluorescence also decreased along the river. In general, the fluorescence index (FI) increased slightly, the humification index (HIX) decreased, and the freshness index (β/α) increased from upstream to downstream. Photo-oxidation and biodegradation experiments were used to determine if the observed changes in DOC composition along the river could be driven by these biogeochemical alteration processes. In two-week natural sunlight photo-oxidation experiments the DOC concentration did not change, while the SUVA254 and TF decreased. In addition, the FI and ‘freshness’ increased and HIX decreased during photo-oxidation. Photo-oxidation can explain the upstream to downstream trends for TF, FI, HIX, and freshness observed in river water. Serial photo-oxidation and biodegradation experiments were performed on water collected from three sites along the Colorado River. Bulk DOC concentration in all samples decreased during the biodegradation portion of the study, but DOC bioavailability was lower in samples that were photo-oxidized prior to the bioavailability study. The upstream to downstream trends in DOC concentration and composition along the river can be explained by a combination of photo-chemical and microbial degradation. The bulk DOC concentration change is primarily driven by microbial degradation, while the changes in the composition of the fluorescent DOC are driven by photo-oxidation. / Dissertation/Thesis / Masters Thesis Chemistry 2015

Abstract Peatland drainage affects about half the peatland area in Finland. Drainage changes natural peatland hydrology and affects water quality through effects on peat decomposition, mineralization, and enhanced mobilization. Runoff water from degraded peatlands transports metals and nutrients and impairs downstream water quality. Peatland restoration through drain blocking can reverse or minimize the negative effects and return degraded peatlands to their natural state over time. In this thesis, a before-after-control-impact study was applied at national scale to 44 boreal peatlands representative of a south-north boreal climate gradient, to study peatland watertable and pore water quality responses to drainage and restoration. Runoff dynamics, watertable levels, and associated characteristics were studied after peatland forestry drainage and subsequent restoration at seven sites. Analysis of watertable-related hydrological responses of 24 drained and restored sites and 19 undisturbed control sites revealed that restoration generally returned watertable levels and fluctuations at restored sites to near-undisturbed levels. This created favorable high-watertable conditions under which peatland species typically flourish. Examination of drainage/restoration effects on local geochemical conditions by studying pore water quality at the same sites revealed that, compared with undisturbed sites, forestry drainage increased dissolved organic carbon (DOC), total phosphorus (Ptot), and total nitrogen (Ntot). Nutrient concentrations continued to increase in the first year after restoration because of significant peatland disturbance, but DOC and nutrient concentrations declined to near-undisturbed levels over time. Watertable level, soil and air temperature, peatland class, and trophic level influenced pore water quality. An investigation of catchment-scale runoff processes in response to drainage and restoration revealed the complexity of runoff dynamics in peatlands. The amount of event runoff water varied between sites, but disturbed sites had higher mean runoff efficiency than undisturbed sites. Raising the watertable increased mean runoff efficiency compared with drained and undisturbed control sites, as shown by higher mean event runoff coefficient. In periods of no rainfall, low flow in all treatment conditions (disturbed, restored, undisturbed) was similar. During rainfall, the drainage networks at disturbed sites created short flow paths and water reached the outlets faster. Watertable-related storage (i.e., specific yield) at disturbed sites was significantly smaller than at other sites, but restoration raised the watertable to near-undisturbed levels into the layer of less decomposed and significantly higher specific yield. Comparing the success of restoration against peatland ecological functions revealed some improvements to restoration techniques that could improve restoration efficiency. However, better hydrological indicators of peatland disturbance are needed. / Tiivistelmä Suomessa on ojitettu iso pinta-ala turvemaita. Ojituksen seurauksena turvemaiden hydrologia on muuttunut ja valumavesien laatu heikentynyt orgaanisen aineksen hajoamisen, mineralisaation ja ravinteiden liikkeellelähdön seurauksena. Valumavedet sisältävät usein metalleja ja ravinteita, jotka heikentävät alapuolisten vesistöjen laatua ja ekologista tilaa. Turvemaiden ennallistaminen ojia tukkimalla tai patoamalla voi vähentää näitä haitallisia vaikutuksia ja palauttaa suoekosysteemin luonnollisen toiminnan ajan saatossa. Tässä väitöstyössä hyödynnettiin kansallista soiden ennallistamisen monitorointiverkostoa, jossa on vedenlaadusta, valunnasta ja vesipintojen korkeudesta aineistoa ennen ja jälkeen soiden ennallistamisen sekä vastaavaa aineistoa luonnontilaisilta vertailualueilta. Tämä aineisto mahdollisti ojituksen ja ennallistamisen hydrologisten vaikutusten tutkimisen ”Ennen-Jälkeen-Kontrolli” – asetelmalla. Tutkimuksessa oli 44 tutkimuskohdetta, jotka edustivat kattavasti Suomen eri ilmastovyöhykkeitä. Näistä seitsemällä kohteella tutkittiin myös valunnan muodostumisen dynamiikkaa turvemetsätalousmailla, ennallistetuilla soilla sekä luonnontilaisilla soilla. Tutkimuksen havaittiin, että ennallistamisen seurauksena vesipintojen taso ja vaihtelu palautui (24 kohdetta) lähelle luonnon tilaa (19 kohdetta). Tulos osoittaa, että kunnostus mahdollistaa suoekosysteemille tyypillisten kasvien palautumisen. Vedenlaatuun liittyvät selvitykset sen sijaan osoittivat, että ojituilla alueilla liuennut orgaaninen hiili (DOC), kokonaisfosfori (Ptot) ja kokonaistyppi (Ntot) pitoisuudet olivat korkeita huokosvesissä. Ravinnepitoisuudet kohosivat edelleen ensimmäisenä vuotena ennallistamisen jälkeen, sillä varsinaiset ennallistamistoimet (puiden kaato, ojien tukkiminen) aiheuttivat häiriötä alueella. Tästä huolimatta DOC ja ravinnepitoisuudet laskivat lähemmäksi luonnontilaisia vertailualueita seuraavina vuosina. Aineiston perusteella, vesikorkeus, maaperän ja ilman lämpötila, suotyyppi ja suon ravinnetaso vaikuttivat veden laatuun. Valunnan vasteet valuma-alueella osoittivat monimutkaisia valunta-sadantaprosesseja turvemailla. Nuoren veden osuus valunnasta sateiden jälkeen vaihteli suuresti tutkimuskohteilla, mutta ojitetuilla/myöhemmin ennallistetuilla kohteilla oli keskimääräistä suurempi valunnan osuus kuin luonnontilaisilla vertailualueilla. Vesikorkeuden nosto ennallistuksessa lisäsi valunnan määrää verrattuna ojitettuun tilanteeseen tai luonnontilaiseen tilanteeseen. Ajanjaksoilla, ilman sadantaa, valuntaprosessit olivat hyvin samankaltaiset ojitetuilla ja myöhemmin ennallistetuilla sekä luonnontilaisilla vertailualueilla. Sateiden jälkeen ojaverkosto muodosti lyhyitä virtausreittejä ja viipymää valuma-alueella. Vesivarastoa kuvaava ominaisantoisuus oli ojitetuilla aluilla merkittävästi heikompi kuin luonnontilaisilla kohteilla. Ennallistaminen vedenkorkeutta nostamalla sen sijaan näkyi merkittävästi korkeampana ominaisantoisuutena. Tätä selittää heikommin maatunut turvekerros suon pinnalla. Työn tulokset edistävät tietoa suokunnostuksen hydrologiasta. Tuloksia voidaan käyttää arvioimaan ja suunnittelemaan soiden ennallistamisen toimenpiteitä ja vaikutuksia.

A crescente contaminação dos sistemas de água doce com milhares de compostos químicos naturais e industriais é um dos principais problemas ambientais enfrentados pela humanidade. Embora a maioria destes compostos esteja presente em baixas concentrações, muitos deles podem causar efeitos danosos à saúde. Adicionalmente ao aumento da poluição, com a descarga de fertilizantes, pesticidas, fármacos, detergentes, derivados de petróleo, entre outros, grande parte das instalações para tratamento de água no Brasil opera com sistema convencional, não atuando de forma eficiente na remoção desses microcontaminates. Carvão ativado em pó (CAP) e granular (CAG) tem sido utilizados em muitos países para remoção de microcontaminantes e substâncias que causam gosto e odor na água. No Brasil já foram desenvolvidas diversas pesquisas com o emprego de CAP para remoção de gosto e odor e alguns contaminantes específicos de águas de abastecimento. Neste trabalho foi testado um CAG produzido a partir de cascas de coco para remoção por adsorção de microcontaminates orgânicos de águas de abastecimento. A água utilizada nos experimentos foi coletada no ponto de captação da Estação de Tratamento de Água (ETA) Lomba do Sabão. Para a caracterização da capacidade adsortiva do carvão foram realizados seis ensaios de isotermas de adsorção e quatro ensaios em colunas de leito fixo, projetada com base na norma ASTM D 3922. Os microcontaminantes orgânicos foram quantificados pela concentração de carbono orgânico dissolvido (COD), medido em analisador de carbono orgânico e por absorbância em espectofotômetro em comprimento de onda de 254nm. Os resultados indicam que o carvão utilizado tem baixa capacidade de adsorver a mistura de microcontaminantes presentes na água de abastecimento, quantificados como COD. Isto se deve, provavelmente, a falta de afinidade entre muitos destes compostos e o carvão. / Pollution growth in water bodies brought by daily discharge of thousands of chemicals from anthropogenic sources is one of the main environmental issues confronting humankind. Although most of these chemicals are present in very low concentrations, they can still be hazardous.to health. Additionally to the increasing levels of pollution brought by discharges of fertilizers, pesticides, prescription drugs and pharmaceuticals, detergents, and petroleum derivatives, among others, the standard processes that are used in drinking water treatment plants in Brazil are not effective to remove these micropollutants. Powdered (PAC) and granular (GAC) activated carbon have been used in many countries to remove micropollutants and taste and odor-causing substances from water. In Brazil, research has been made using PAC to remove taste and odor substances and specific micropollutants from water. In this research, GAC produced from coconut shells was used to test the removal of organic micropollutants present in source water by adsorption. Water used in this research was collected at the intake of Lomba do Sabão drinking water treatment plant in Porto Alegre. In order to assess the GAC adsorption capacity, six isotherm (batch) and four column (continuous flow) assays were performed according to ASTM D 3922 standard. Organic micropollutants were quantified by the concentration of dissolved organic carbon (DOC) and by ultraviolet absorption at 254 nm wavelength. The results suggest that the tested GAC have limited capability in adsorb the complex mixture of micropollutants that are present in source water, as measured by DOC. This is probably caused by lack of affinity between many micropollutants present in the mixture and the carbon.

A crescente contaminação dos sistemas de água doce com milhares de compostos químicos naturais e industriais é um dos principais problemas ambientais enfrentados pela humanidade. Embora a maioria destes compostos esteja presente em baixas concentrações, muitos deles podem causar efeitos danosos à saúde. Adicionalmente ao aumento da poluição, com a descarga de fertilizantes, pesticidas, fármacos, detergentes, derivados de petróleo, entre outros, grande parte das instalações para tratamento de água no Brasil opera com sistema convencional, não atuando de forma eficiente na remoção desses microcontaminates. Carvão ativado em pó (CAP) e granular (CAG) tem sido utilizados em muitos países para remoção de microcontaminantes e substâncias que causam gosto e odor na água. No Brasil já foram desenvolvidas diversas pesquisas com o emprego de CAP para remoção de gosto e odor e alguns contaminantes específicos de águas de abastecimento. Neste trabalho foi testado um CAG produzido a partir de cascas de coco para remoção por adsorção de microcontaminates orgânicos de águas de abastecimento. A água utilizada nos experimentos foi coletada no ponto de captação da Estação de Tratamento de Água (ETA) Lomba do Sabão. Para a caracterização da capacidade adsortiva do carvão foram realizados seis ensaios de isotermas de adsorção e quatro ensaios em colunas de leito fixo, projetada com base na norma ASTM D 3922. Os microcontaminantes orgânicos foram quantificados pela concentração de carbono orgânico dissolvido (COD), medido em analisador de carbono orgânico e por absorbância em espectofotômetro em comprimento de onda de 254nm. Os resultados indicam que o carvão utilizado tem baixa capacidade de adsorver a mistura de microcontaminantes presentes na água de abastecimento, quantificados como COD. Isto se deve, provavelmente, a falta de afinidade entre muitos destes compostos e o carvão. / Pollution growth in water bodies brought by daily discharge of thousands of chemicals from anthropogenic sources is one of the main environmental issues confronting humankind. Although most of these chemicals are present in very low concentrations, they can still be hazardous.to health. Additionally to the increasing levels of pollution brought by discharges of fertilizers, pesticides, prescription drugs and pharmaceuticals, detergents, and petroleum derivatives, among others, the standard processes that are used in drinking water treatment plants in Brazil are not effective to remove these micropollutants. Powdered (PAC) and granular (GAC) activated carbon have been used in many countries to remove micropollutants and taste and odor-causing substances from water. In Brazil, research has been made using PAC to remove taste and odor substances and specific micropollutants from water. In this research, GAC produced from coconut shells was used to test the removal of organic micropollutants present in source water by adsorption. Water used in this research was collected at the intake of Lomba do Sabão drinking water treatment plant in Porto Alegre. In order to assess the GAC adsorption capacity, six isotherm (batch) and four column (continuous flow) assays were performed according to ASTM D 3922 standard. Organic micropollutants were quantified by the concentration of dissolved organic carbon (DOC) and by ultraviolet absorption at 254 nm wavelength. The results suggest that the tested GAC have limited capability in adsorb the complex mixture of micropollutants that are present in source water, as measured by DOC. This is probably caused by lack of affinity between many micropollutants present in the mixture and the carbon.

Increased DOC and Fe concentrations from terrestrial landscapes has led to the browning of boreal surface waters. The negative societal and ecological impacts of brownification are increased cost of water purification, increased presences of algae and cyanobacteria, loss of ecosystem services and reduced recreational value. Impacts of climate change, changes in land use and reduced sulfur deposition have been identified as drivers of brownification. While it has been recognized that DOC and Fe from terrestrial landscapes is increasing, little has been done to understand the impact of different land use practices on brownification. This research aims at evaluating the DOC and Fe runoff from spruce plantations, clear-cuts and wetland landscapes and determining the export of DOC from these landscapes into humic lakes. To do that, streams running through these three different land use types were sampled for water colour, pH, temperature, conductivity, DOC and Fe both at upstream and downstream of each land use type. Further, water discharge was calculated with the help of flow speed measurements and stream profiling (width, depth and channel shape). DOC (but not Fe) concentrations changed significantly depending on land use type. Wetlands lead to reduced DOC concentrations, whereas especially spruce plantations lead to increased stream water DOC concentrations.

Blackwater rivers and lakelets are a common feature of the landscape in the South Western Cape. Contrastingly, white rivers can also be found in the region. Key to the colour of blackwaters is the increased presence of dissolved organic carbon. The vegetation of the regions is known to posses' large amounts of polyphenols and potentially low microbial decomposition. Therefore, are the plant-soil dynamics a possible answer to variation in river colour? To answer this, the chemical correlates of rivers in the region, along with the in vitro leaching of the fynbos vegetation compared to other types and the effects of nutrient fertilisation on microbial activity in soil were determined. The results revealed that organic carbon, Fe and pH are significantly correlated with blackwaters. The Fe in the water appears to be bound to humic compounds. Fynbos vegetation is able to produce greater concentrations of polyphenol leachates (315 mg/l humic acid) compared to savanna species (246 mg/ humic acid) over a four-day period. P fertilisations increased the concentrations of humic acids from 30 mg/1 to 200 mg/l in some soils through their affinity to bind with humic compounds. The N fertilisations moderately increased the humic acid concentrations and in some cases lowered the concentration by 10 mg/l, indicating that it provided a nutrient source to the microbes for carbon breakdown. The interactions between humic compounds, nutrients and Fe are key to the formation of blackwaters in the region. Attached to this is the limited decomposition that takes place due to nutrient limitations. Therefore, the interactions between the carbon leached from the vegetation and below ground activities are determinants of water colour in the South Western Cape.

One of the defining characteristics of our current epoch—the Anthropocene—is modification of nutrient cycles. At regional to global scales, humans have fundamentally reshaped the availability of carbon, nitrogen, and phosphorus. These changes are particularly apparent in freshwater ecosystems, which receive surface and groundwater inputs of nutrients from agriculture, fossil fuel use, and wastewater. In this thesis, I investigated how the addition of nutrients affects microbial community and biogeochemistry in two extreme environments: the hypereutrophic shallow Utah Lake and nutrient-limited Arctic permafrost streams. In my first chapter, I used bioassay and dilution bioassay experiments to identify what factors control harmful algal blooms in Utah Lake. Specifically, I measured phytoplankton and cyanobacteria growth, cyanotoxin production, and aquatic N-fixation potential. I included physical factors, such as temperature, light, nutrient concentrations, and pH, as well as biological factors, such as top-down control by zooplankton grazers. Phytoplankton showed a threshold behavior at 0.005 mg/L for soluble reactive phosphorus and 0.14 mg/L for dissolved inorganic nitrogen. Surprisingly, nitrogen fixation rates were only high in active bloom samples and were augmented by the addition of both nitrogen and phosphorus. Also contrary to our hypothesis, zooplankton preferentially grazed cyanobacteria over total phytoplankton. In my second chapter, I investigated how permafrost degradation might influence dissolved organic matter (DOM) in Arctic stream networks. Specifically, I used nutrient and labile carbon additions to simulate the effects of permafrost thaw DOM degradation and microbial community in three distinct permafrost-covered catchments on the North Slope of Alaska. The alpine catchment had higher biodegradability but lower DOM concentration across seasons compared with the lake-influenced and tundra catchments. For all catchments, there were strong seasonal changes in microbial community and distinct responses to nutrient addition. The addition of nutrients stimulated DOM biodegradation in the late season—the period of the year when permafrost DOM release typically occurs. Microbial communities differed by catchment type, but overall diversity was similar. Together, these experiments highlight the diverse downstream consequences of human alteration of global carbon, nitrogen, and phosphorus cycles. Even in extreme systems, alteration of the microbial community regulating many of these cycles has potential to exacerbate ecosystem and climate change, so understanding our influence over biogeochemical cycles and microbial interactions is vital for informing future management practices and planetary boundaries.

Antihistamines are a group of pharmaceuticals that enter the environment and may affect microorganisms that regulate decomposing of organic matter and the release of carbon and nitrogen from soils. In this study I investigated if the antihistamine fexofenadine decreases the concentration of dissolved organic carbon (DOC) and dissolved organic nitrogen (DON) from humus. I used humus from two vegetation types (heath and meadow), and used a batch experiment approach, where humus was mixed with fexofenadine solutions (2000 ng/L and 20 000 ng/L). After ten days in room temperature, the samples with fexofenadine were compared with batches containing pure water solutions (control). I found differences in the concentration of DOC, DON and pH that were dependent on the studied vegetation types. There were higher concentrations of DOC and DON in heath (35.9 mg/L and 2.0 mg/L) than in the more nutrient rich meadow (9.2 mg/L and 0.5 mg/L). The latter vegetation type did also have a higher pH. In contrast to my hypothesis, the concentration of DOC and DON was not significantly affected by the fexofenadine. However, if considering a 90%-level of significance, there were a significant interaction effect where concentration of DOC decreased in meadow and increased it in heath. A possible vegetation specific effect of fexofenadin seems plausible as microbial biomass and activity in the vegetation types are known to differ. My findings cannot exclude that fexofenadine stimulates degradation of DOC in the more microbial active meadow humus, but not in the humus of heath where activities are lower.

There are several incentives for using bottom ash from municipal solid waste incineration (MSWI bottom ash) as a construction material, such as for road construction. These incentives include decreased disposal of material on landfills and a reduced amount of raw material extracted for road building purposes. However, one of the main obstacles to utilising the material is uncertainties regarding its environmental properties. The overall objective of this thesis is to describe the potential environmental impacts of utilising MSWI bottom ash in constructions and to improve the tools for environmental assessments. An environmental systems analysis (ESA) approach based on a life cycle perspective was outlined and used in a case study, with the aim of describing the differences in resource use and emissions that can be expected if crushed rock in the sub-base of a road in the Stockholm region in Sweden were to be substituted by MSWI bottom ash. The whole life cycle of the road was taken into account and the alternative disposal of the bottom ash was included. It was found that the studied alternatives would cause different types of potential environmental impact; whereas the conventional alternative with only crushed rock in the road’s sub-base would lead to larger use of energy and natural resources, the alternative with MSWI bottom ash in the sub-base would lead to larger contaminant leaching. It was concluded that a life cycle approach is needed in order to include both resource use and emissions in the comparison between the two alternative scenarios. The leaching of metals turned out to be the most important environmental aspect for the comparison and in particular the difference in copper (Cu) leaching was shown to be large. However, a large amount of Cu may not pose an environmental threat if the Cu is strongly bound to dissolved organic carbon (DOC). In order to improve the basis for toxicity estimates and environmental risk assessments, and thereby provide better input values for ESAs, the speciation of Cu to DOC in MSWI bottom ash leachate was studied. It was found that Cu to a large extent was bound to DOC, which is consistent with previous research. The results also suggest that the hydrophilic fraction of the MSWI bottom ash DOC is important for Cu complexation and that the pH-dependence for Cu complexation to MSWI bottom ash DOC is smaller than for natural DOC. This implies that models calibrated for natural DOC may give inconsistent simulations of Cu-DOC complexation in MSWI bottom ash leachate. / QC 20101217

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