<p>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.</p><p>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.</p><p>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.</p>

Mature karst topography is well recognized within the hydrology and geology communities to include subterranean fluid pathways that act as turbulent conduits conveying fluid from surface stream sinks called swallets to sources called springs. However, we find that little knowledge has been reported with regards to the transport and fate of terrestrially-derived sediment organic carbon (SOC) within karst watersheds. This study investigated the hypothesis that karst pathways could act as biologically active conveyors of SOC that temporarily store sediment, turnover carbon at higher rates than otherwise considered, and recharge depleted SOC back to the surface stream within the fluvial system. Mixed research methods were applied within a mature karst network. Methods included high resolution measurements of water and sediment characteristics of surface streams, carbon and stable carbon isotope measurements of transported sediment, and numerical modeling of water and sediment pathways. The mixing of sediment during net zero deposition and erosion was investigated in this study using a parameter calibrated to SOC data. Results of this study showed that heterotrophic bacteria in the subsurface conduit oxidized 0.05 tCkm-2y-1 resulting from the temporary storage of terrestrial carbon in the karst conduit. The subsurface conduit transports 0.15 tCkm-2y-1 out of the fluviokarst watershed.

The evaluation of the soil spatial variability using a fast, robust and cheap tool is one of the key steps towards the implementation of Precision Agriculture (PA) successfully. Soil organic carbon (OC), soil total nitrogen (TN) and soil moisture content (MC) are needed to be monitored for both agriculture and environmental applications. The literature has proven that visible and near infrared (vis-NIR) spectroscopy to be a quick, cheap and robust tool to acquire information about key soil properties simultaneously with relatively high accuracy. The on-line vis-NIR measurement accuracy depends largely on the quality of calibration models. In order to establish robust calibration models for OC, TN and MC valid for few selected European farms, several factors affecting model accuracy have been studied. Nonlinear calibration techniques, e.g. artificial neural network (ANN) combined with partial least squares regression (PLSR) has provided better calibration accuracy than the linear PLSR or principal component regression analysis (PCR) alone. It was also found that effects of sample concentration statistics, including the range or standard derivation and the number of samples used for model calibration are substantial, which should be taking into account carefully. Soil MC, texture and their interaction effects are other principle factors affecting the in situ and on-line vis-NIR measurement accuracy. This study confirmed that MC is the main negative effect, whereas soil clay content plays a positive role. The general calibration models developed for soil OC, TN and MC for farms in European were validated using a previously developed vis-NIR on-line measurement system equipped with a wider vis-NIR spectrophotometer (305 – 2200 nm) than the previous version. The validation results showed this wider range on-line vis-NIR system can acquire larger than 1500 data point per ha with a very good measurement accuracy for TN and OC and excellent accuracy for MC. The validation also showed that spiking few target field samples into the general calibration models is an effective and efficient approach for upgrading the implementation of the on-line vis-NIR sensor for measurement in new fields in the selected European farms.

Soil structure influences many chemical, biological and physical processes and it is well established that organic carbon acts as a soil binding agent. However, the precise location of organic matter and carbon in relation to structural features within intact samples is unknown. The sensitivity of organic carbon to decomposition is dependent not only upon its intrinsic chemical recalcitrance, but also its location within the soil structure. Soil structure provides organic carbon with chemical and physical protection, the extent of which varies between structural units. Furthermore soil structure is transient, and is sensitive to both environmental changes and physical disturbance, therefore it is difficult to determine and quantify the impact of this dynamic entity upon the storage of organic carbon. To date the majority of research that has advanced our understanding of the role soil structure plays in the storage of organic carbon, has relied upon some form of fractionation technique to separate aggregates from the bulk soil. However this approach has its disadvantages as much of the soil structure is destroyed; clearly when studying the impact of soil structure upon organic carbon-storage it is advantageous to implement any method that minimises disturbance to the soil structure. This study entails removing intact soil samples (through the use of kubiena tins) from long-term agricultural experimental fields at Rothamsted Research, (Hertfordshire, UK) with the aim of comparing and evaluating the location of organic matter and it’s associated organic carbon, in soils with contrasting organic carbon contents and a well documented land-use history. Thin sections will be analysed by integrating conventional micromorphology, image analysis and sub-microscopy combined with microscale chemical analysis scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS). In doing so a new alternative method for analysing the distribution of organic matter and organic carbon is proposed. It was found that agricultural soils, which are the same in all aspects except total-OC content, differ in total organic matter, water release characteristics, aggregate stability and pore size distribution; therefore these differences could be attributed to the relationship between OC and soil structure. The water release curve, aggregate stability and pore size distribution also differed between soils with similar OC-contents but from different land-uses. The analysis of organic matter within intact soil samples provided evidence for the redistribution of organic matter as it is decomposed within the soil structure, for instance, less decomposed organ and tissue forms were located in or near to soil pores while more decomposed amorphous forms were located within the soil matrix. Since the same pattern of redistribution was observed in both agricultural and grassland soil this is likely to be directed by soil macro and micro fauna. It is concluded that since the location of different forms of organic matter is consistent across all soil, organic matter location is not responsible for creating differences in aggregate stability between treatments. Instead the results indicate that the amount and strength of organic carbon bonds and its hydrophobic properties are responsible. Micromorphology results demonstrated an absence of defined aggregation between treatments. Despite the difficulties in the interpretation of aggregation, the results contradict theories of aggregation, which state that aggregates are formed around “fresh” organic matter and it is argued that OM will undergo substantial decomposition before it acts as core for aggregation. Initial SEM-EDS analysis, has shown that in the soil matrix adjacent to organic matter (plant/organ) fragments there is a heightened concentration of C, indicating that these fragments are acting as a source of organic carbon. Interestingly BC, which represent one of the most recalcitrant C forms is also acting as a source of C, although these initial results suggest to a lesser extent than more labile C-sources. This source of organic carbon could stimulate microbial activity thereby enhancing soil structural stability. Alternatively, the release of liable carbon into soil pores may represent one route by which labile carbon enters sub-soil horizons.

Switchgrass (Panicum virgatum), a perennial C4 grass species, has the capacity to not only improve the quality of the soil in which it grows but also promote soil carbon storage to offset rising atmospheric CO2. This research investigated soil organic carbon (SOC) dynamics beneath switchgrass using natural abundance 13C and soil carbon fractionation following the establishment of this crop in a native and predominantly C3 plant region in southeastern Ontario. I investigated SOC dynamics by sampling adjacent commercial switchgrass fields and appropriate paired control fields at sites where the time since switchgrass establishment varied from 4-11 years. SOC and natural 13C abundance were measured in paired fields to assess management-induced changes in the quantity, source, and turnover time of soil carbon. To better elucidate carbon cycling dynamics over a relatively short time since switchgrass establishment, multiple soil fractionation techniques were applied to better understand carbon dynamics of soil organic matter with various mean residence times. Establishment of switchgrass results in marginal increases in SOC, primarily at sites where intensive soil management (i.e. tillage) practices preceded switchgrass establishment. Changes were observed in some of the more labile SOC pools, as well as in the δ13C values of the bulk soil and soil carbon fractions, indicating that growing switchgrass was causing the incorporation of switchgrass-derived carbon into the soil. Even resistant SOC pools, with turnover times of over 100 years, incorporated significant quantities of switchgrass carbon in 11 years. Annual increases in SOC, however, were less than values reported elsewhere. The potential for soil carbon storage exists, likely due to longer mean residence times of the carbon in soils beneath switchgrass compared with other cultivation systems. Changes in SOC following switchgrass establishment related strongly to the amount of root biomass, time since establishment and prior soil management practices. The decomposition rates derived in this research should be integrated into soil carbon modeling applications intended to support the emergence of switchgrass in southeastern Ontario. The results of my research can advance soil carbon models and be used to make regional assessment of the potential impact of growing switchgrass for bioenergy in southeastern Ontario. / Thesis (Master, Geography) -- Queen's University, 2012-01-30 13:56:06.269

High latitude soils are estimated to store a considerable part of the global pool of soil organic carbon (SOC). Studies of global and regional SOC pools have estimated total inventories in northern Sweden’s subarctic region to fall within 10-50 kg m-2. However, correction factors for stone and boulder content of soils are often overlooked in SOC-studies and soil profiles are commonly normalized to a depth of 1 m, which can result in substantial overestimates of the SOC pool if a large part of the soil volume is occupied by stones/boulders or if the soil depth is shallower than 1 m. This study was performed to quantify SOC in soils of the Torneträsk catchment area using detailed measures of soil depth and stone/boulder contents. Two non-destructive sampling methods, ground penetrating radar (GPR) and rod penetration, were used to measure soil depth and stone and boulder content in the catchment area. Results show that average soil depth (n = 52344) varied between 0.95 – 2.14 m depending on elevation and the average mire depth was 0.63 m. Stone and boulder content of the soil was estimated to 49 – 68 % depending on elevation. The results were added to existing carbon and soil density data from the Torneträsk catchment area and total SOC inventories were calculated to 6.8 – 13.1 kg m-2. The results of this study indicate that previous studies on regional and global scale may have overestimated the SOC pools in the subarctic regions of northern Sweden.

Carbon/phosphorus ratios for late Devonian-early Mississippian marine black shales along a transect from the Illinois Basin, across the Cumberland Saddle, and into the Appalachian Basin were evaluated to assess the role of productivity in organic carbon accumulation. Phosphorus is a key limiting nutrient for biological productivity in marine environments and may be regenerated preferentially relative to organic carbon, the amount of regeneration possibly being related to bottom-water anoxia. A positive feed-back mechanism (more specifically, productivity-anoxia feedback or PAF) has been proposed between water-column anoxia, high benthic regeneration of phosphorus, and marine productivity. This regeneration of phosphorus under anoxic conditions and overturn of surface waters has been proposed as an explanation for enhanced organic matter accumulation in the Appalachian Devonian Basin. The Cumberland Saddle is a structurally low segment of the Cincinnati Arch that lies at the crest of the arch between the Jessamine and Nashville domes that connects the Illinois and Appalachian basins. C/P data for two cores in the Illinois Basin, four cores across the Cumberland Saddle, and two cores in the Appalachian Basin are discussed in light of the productivity-anoxia feedback model.

The long-term fate of hydrocarbons in the Gulf of Mexico (GOMx) following the 2010 Deepwater Horizon oil spill has yet to be fully characterized. Elemental (% C and % N), stable isotopes (δ13Corganic), and polycyclic aromatic hydrocarbon (PAH) molecular signatures were investigated in shelf and slope sediments collected in October 2010 and 2011 to gain insight into processes affecting the distribution and fate of spilled Macondo oil. Particulate organic carbon (POC) ranged between 1.55 and 2.22 wt. % in 2010 and 0.55 and 2.06 % in 2011 while the corresponding δ13Corganic ranges were from -23.37 to -20.77 ‰ (vs. PDB) in 2010, and -22.68 to -20.75 ‰ (vs. PDB) in 2011. Ranges of total polycyclic aromatic hydrocarbon (TPAH) concentrations were from 72.57 to 7,543.53 ng/g in 2010 and 25.55 to 16,582.77 ng/g in 2011. The range of measured values represented significant deviations from previous background measurements. This provided the basis for concluding that the Macondo spill altered the “background” organic carbon and hydrocarbon signature, that Macondo oil has weathered and/or biodegraded in the year following the spill, and that a significant spatial trend of hydrocarbons extended from the Macondo well across the northern GOMx in October 2010 and 2011.

Perfluoroalkylated substances (PFASs) are a group of synthetic compounds that have gained growing attention due to their environmental persistence, toxicity and their potential to bioaccumulate. Even though PFASs are not occurring naturally in our environment, they are globally distributed and can be found ubiquitously in air, water, soil, wildlife as well as in humans. PFASs have primarily been used, due to their unique properties of being both hydrophilic and hydrophobic, as surfactants in numerous products such as firefighting foams, paint, leather and textile coating. The occurrence of PFASs in drinking water as well as in wastewater makes it important to develop effective techniques to remove these compounds from drinking water sources and wastewater. To be able to effectively remove PFASs from drinking water and wastewater it is important to understand which treatment process is most efficient and how the removal efficiency is affected by the physicochemical properties of PFASs and characteristics of water. In this study, the removal efficiency of PFASs was investigated using six different water types with varying dissolved organic carbon (DOC) character. Four different treatment techniques were evaluated including anion exchange using MIEX® resins, coagulation with iron (III) chloride (FeCl3), adsorption using powdered activated carbon (PAC) and nanofiltration (NF) membrane. The batch experiments were performed in laboratory-scale for 14 individual PFASs including C3-11, C13 perfluoroalkyl carboxylic acids (PFCAs), C4, C6, C8 perfluoroalkyl sulfonic acids (PFSAs) and perfluorooctane sulfonamide (FOSA). The results showed that the removal efficiency of PFASs was dependent on both perfluorocarbon chain length as well as functional group, with an increase in removal efficiency with increased perfluorocarbon chain length. Short-chained PFASs (C!6) were removed in less extent than the long chained PFASs for all treatment techniques. Amongst the four treatment techniques investigated, NF membrane exhibited the best removal efficiency for both short- and long chained PFASs (on average, 51%). Lower removal efficiencies for PFASs were observed for MIEX (33%) &lt; FeCl3 (16%) &lt; PAC (14%). However, all tested treatment techniques used in this study exhibited generally low removal efficiency (&lt; 78%), in particular for the short-chained PFASs (C!6, &lt; 41%) Results using three different doses of PAC (i.e. 20, 50, 100 mg L-1) showed an increase in removal (i.e. 2.2-41%, 8.0-78% and 12-92% respectively) with increasing dose. No significant trends were found between PFAS removal and DOC removal for any of the treatments (p&lt;0.05, student t-test). However, the removal efficiency was different of the six different water types, which indicates that the DOC characteristics (i.e. Freshness, humification index, pH and absorbance) have an influence on the removal efficiency of PFASs in water. / Perfluoroalkylerade ämnen (PFASer) är en grupp syntetiska ämnen som har fått allt större uppmärksamhet den senaste tiden då de har visat sig vara persistenta, toxiska och bioackumulerande. Även om PFASer inte förekommer naturligt i vår miljö är de globalt fördelade och kan återfinnas i luft, vatten, mark, djur och hos människor. PFASer har främst använts, på grund av sina unika egenskaper att vara både hydrofila och hydrofoba, som tensider i många produkter såsom brandsläckningsskum, färg, läder och textil. Förekomsten av PFASer i dricksvattentäkter och i många reningsverk gör det viktigt att utveckla effektiva metoder för att ta bort dessa föreningar i vattenreningsverk. För att effektivt kunna avlägsna PFASer från dricks- och avloppsvatten är det viktigt att ha kunskap om vilken behandlingsmetod som är effektivast och hur reningseffektiviteten påverkas av ämnenas fysikalisk-kemiska egenskaper och vattnets karaktär.   Syftet med denna studie var att undersökta reningseffektiviteten för PFASer i sex olika vatten innehållande olika typer av löst organiskt kol (DOC). Detta undersöktes för fyra olika behandlingsteknikert; jonbyte med MIEX®, koagulering med järnklorid (FeCl3), adsorption med hjälp av pulveriserat aktivt kol (PAC) och nanofiltrering. Försöken gjordes små skaligt i laboratorie och 14 olika PFASer undersöktes; C3-11,13  perfluoralkyl karboxylsyror (PFCAer), C4, C6, C8, perfluoralkyl sulfonsyror (PFSAer) och perfluoroktan sulfonamid (FOSA). Resultaten visar att reningseffektiviteten för PFASer var beroende av både den perfluorerade kolkedjans längd och funktionell grupp, med en ökning av reningseffektivitet med längre perfluorerad kolkedja. PFASer med kort perfluorerad kolkedja (C≤6) renades i mindre utsträckning än PFASer med lång perfluorerad kolkedjade; detta gällde för alla behandlingstekniker. Bland de fyra behandlingstekniker som undersöktes uppvisade nanofiltreringen den bästa reningseffektiviteten för PFASer med både korta och långa kolkedjor (i genomsnitt, 51%.). Lägre reningseffektivitet för PFASer observerades för MIEX®(33%), &lt; FeCl3(16%) &lt; PAC (14%). Totalt sett erhölls en relativt låg reningseffektivitet (&lt;78%) för samtliga reningstekniker, speciellt för de kortkedjade PFASer (C£6, &lt; 41%). Resultat från försök med tre olika doser PAC (e.g. 20, 50, 100 mg L-1) visade på en ökad reningseffektivitet (2,2-41%, 8,0-78% och 12-92%) med ökad dos PAC. Inga signifikanta trender kunde urskiljas vad gäller reningseffektivitet av PFASer och rening av DOC (p&lt;0.05, student t-test), detta gällde för samtliga behandlingstekniker. Det fanns dock tydliga skillnader i reningseffektivitet mellan de sex olika vattentyperna vilket indikerar på att DOC egenskaperna (Freshnessindex, humifieringsindex, pH, absorbans) har en påverkan på reningseffektiviteten för PFASer i vatten.

The skin of many fishes contains large epidermal club cells (ECCs) that are known to release chemicals (alarm cues) that warn other fishes of danger. Initial research on ECCs focussed on their role in predator avoidance behaviour, however later research revealed that these cells might also have immune functions. Anthropogenic activities have dramatically increased over the past decades, with the consequence that many organisms simultaneously get exposed to multiple environmental stressors. We have seen considerable reductions in stratospheric ozone with a concomitant increase in global ultraviolet radiation (UVR). Metal pollution associated with industrial activity is also increasing on a global scale. Cadmium (Cd) is one such ubiquitous pollutant which is known to be toxic to organisms at extremely low concentrations. The main goal of my PhD research was to understand how multiple environmental stressors play a role in altering ECC investment and chemically-mediated predator-prey interactions by indirectly elucidating the evolutionary role of ECCs. The first experiment investigated the effects of in vivo ultraviolet radiation (UVR) exposure on ECC investment, physiological stress responses and potency of alarm cues in fathead minnows (Pimephales promelas). Subsequently, I investigated the interactive effects of UVR and/or waterborne cadmium (Cd) exposure using the same end points. I found that minnows exposed to UVR, either in the presence or absence of Cd, showed consistent decrease in ECC investment compared to non-exposed controls. There was a significant increase in cortisol levels of UVR exposed minnows compared to unexposed minnows. However, the combined exposure of UVR and Cd reduced cortisol levels relative to that in UVR only exposure. Surprisingly, there was no difference in the potency of the cues prepared from the skin of UVR and/or Cd exposed or non-exposed fish indicating that UVR and/or Cd exposure combined may have little influence on chemically-mediated predator-prey interactions. In aquatic systems, much of the negative effects of UVR are minimized by dissolved organic carbon (DOC) which is known to attenuate rates of UVR across the water column. In my third study, I investigated if DOC played a role in ameliorating the effects of in vivo UVR exposure on physiological stress and ECC investment in fathead minnows. I used two sources of DOC, a commercial soil based DOC (Sigma Aldrich Humic Acid) and a terrigenous source of DOC (Luther Marsh Natural Organic Matter). I found that fish exposed to UVR, in the presence of either source of DOC, in the presence and absence of UV blocking filter, maintained high ECC investment and reduced cortisol levels compared to fish exposed to UVR only. Studies that have examined factors that influence ECC investment have often been hampered by large variation in baseline levels of ECC. The larger the baseline variation in ECC number, the more difficult it is to elucidate factors responsible for changes in ECC investment. While I did not find this problematic in my work with UVR and Cd, others have failed to find effects in manipulative experiments. Consequently, my fourth study examined between and within variation in ECC investment across multiple sites in Saskatchewan and tried to investigate if holding fish under controlled laboratory conditions for up to 28 days would help reduce variation in ECC investment between and within populations. I found some evidence that I could reduce within population variation in ECC investment through time, but could not reduce among-population variation in mean ECC investment.