| 1. |
- Ericson Jogsten, Ingrid, 1980-
(author)
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Assessment of human exposure to per- and polyfluorinated compounds (PFCs) : exposure through food, drinking water, house dust and indoor air
- 2011
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Doctoral thesis (other academic/artistic)abstract
- Per- and polyfluorinated compounds (PFCs) are detected in humans worldwide but all sources of human exposure have not been fully characterized. The aim of this thesis was to evaluate the contributions from food, water, air and dust as sources for human PFC exposure in the general population. Per- and polyfluorinated compounds (PFCs) are detected in humans worldwide but all sources of Up to 27 PFCs were determined at trace levels in blood (ng/mL), water (ng/L), foods (ng/g), dust (ng/g) and air (pg/m3) in a selected Catalan population and PFC intake was estimated from the measured PFC concentrations of the different sources of exposure. The major compounds detected in human blood of the studied population were perfluorooctane sulfonate (PFOS; 7.6 ng/mL), perfluorohexane sulfonate (PFHxS; 3.6 ng/mL) and perfluorooctanoic acid (PFOA; 1.8 ng/mL). In general, PFOS was also the major compound detected in most sources of exposure. Food was found to be the dominant pathway for human PFC exposure accounting for more than 70 % of the total intake of both PFOS and PFOA. In the most populated area (the Barcelona Province) where the highest levels were measured, tap water can contribute to the total exposure substantially with more than 50 % for adults. Indoor sources were negligible in the selected area for most PFCs when compared to food and water intake, except for toddlers under a worst case scenario where contribution from dust and food intake were equal (19 %). Pharmacokinetic (PK) modelling resulted in exposure of 103 ng PFOS/day and 33 ng PFOA/day of adults from the internal PFC blood concentrations. This agrees well with the intake estimated from external exposure through food, drinking water, house dust and indoor air of 80 ng PFOS/day and 32 ng PFOA/day and evidently all major exposure sources for the general population were included (in this study).
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| 2. |
- García García, Sandra, 1977-
(author)
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Generation, stability and migration of montmorillonite colloids in aqueous systems
- 2010
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Doctoral thesis (other academic/artistic)abstract
- In Sweden the encapsulated nuclear waste will be surrounded by compacted bentonite in the granitic host rock. In contact with water-bearing fractures the bentonite barrier may release montmorillonite colloids that may be further transported in groundwater. If large amounts of material are eroded from the barrier, the buffer functionality can be compromised. Furthermore, in the scenario of a leaking canister, strongly sorbing radionuclides, can be transported by montmorillonite colloids towards the biosphere. This thesis addresses the effects of groundwater chemistry on the generation, stability, sorption and transport of montmorillonite colloids in water bearing rock fractures. To be able to predict quantities of montmorillonite colloids released from the bentonite barrier in contact with groundwater of varying salinity, generation and sedimentation test were performed. The aim is first to gain understanding on the processes involved in colloid generation from the bentonite barrier. Secondly it is to test if concentration gradients of montmorillonite colloids outside the barrier determined by simple sedimentation experiments are comparable to generation tests. Identical final concentrations and colloid size distributions were achieved in both types of tests. Colloid stability is strongly correlated to the groundwater chemistry. The impact of pH, ionic strength and temperature was studied. Aggregation kinetics experiments revealed that for colloid aggregation rate increased with increasing ionic strength. The aggregation rate decreased with increasing pH. The temperature effect on montmorillonite colloid stability is pH-dependent. At pH≤4, the rate constant for colloid aggregation increased with increasing temperature, regardless of ionic strength. At pH≥10, the aggregation rate constant decreased with increasing temperature. In the intermediate pH interval, the aggregation rate constant decreased with increasing temperature except at the highest ionic strength, where it increased. The relationship between the rate constant and the ionic strength allowed the critical coagulation concentration (CCC) for Na- and Ca-montmorillonite to be determined. In order to distinguish the contribution of physical filtration and sorption to colloid retention in transport, the different retention mechanisms were quantified. Sorption on different representative minerals in granite fractures was measured for latex colloids (50, 100, 200 nm) and montmorillonite colloids as a function of ionic strength and pH. Despite of the negative charge in mineral surfaces and colloids, sorption was detected. The sorption is correlated to the mineral point of zero charge and the zeta potential of the colloids, and increases with increasing ionic strength and decreasing pH. In transport experiments with latex colloids in columns packed with fracture filling material, the retention by sorption could clearly be seen. In particular at low flow rates, when the contact time for colloids with the mineral surfaces were the longest, sorption contributed to retention of the transport significantly. The retention of latex colloids appeared to be irreversible in contrary to the reversible montmorillonite colloid retention. Generation, stability and sorption of the montmorillonite colloids are controlled by electrostatic forces; hence, the results were in qualitative agreement with DLVO.
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| 3. |
- Greis, Christina, 1975-
(author)
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Rapid analysis of actinide isotopes using quadrupole ICP-MS for emergency preparedness and environmental monitoring
- 2007
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Doctoral thesis (other academic/artistic)abstract
- Transuranium elements in the environment are mainly derived from nuclear weapons testing and the nuclear fuel cycle. Of growing concern are illicit nuclear trafficking and the threat of terror acts. The development of rational methods, for environmental monitoring and for tracing sources of nuclear and radioactive materials in the environment, is constantly required. Traditionally, the actinides have been determined by radiometric techniques. These analyses can be time consuming for elements at low concentrations and with long half-lives. This thesis addresses the determination of actinides, especially plutonium, in environmental samples with ICP-QMS (inductively coupled plasma quadrupole mass spectrometry). The ICP-QMS instrument was equipped with an USN (ultrasonic nebuliser), which proved to be a successful combination for the determination of plutonium at low concentrations in acidified solutions after separation with anion exchange. The detection limit for plutonium was in the range 10-30 pg/l with a RSD of 1-10%. The suitability of chemical separation was evaluated for anion exchange, liquid-liquid-extraction and extraction chromatography. The outlined procedure, including sample dissolution, chemical separation and analysis, for determination of actinides in environmental matrices proved to be accurate and reliable. Quality assurance of the procedure was performed during an intercomparison exercise and with reference materials. The detection accuracy has also been validated with α-spectrometry and ICP-SFMS. The procedure has been applied to saline sediments and fresh water sediments as well as several fresh water matrices.
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| 4. |
- Rotander, Anna, 1978-
(author)
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Monitoring persistent organic pollutants (POPs) in sub-Arctic and Arctic marine mammals, 1984 - 2009
- 2011
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Doctoral thesis (other academic/artistic)abstract
- The Arctic has become an important indicator region for assessing persistence and bioaccumulation properties of persistent organic pollutants (POPs). This thesis is aimed at evaluating the occurrence of persistent halogenated POPs in seven species of sub-Arctic and Arctic marine mammals over a 25-year period. The emphasis is on studying temporal variations in concentration of three categories of POPs, including naturally occurring organobromine compounds. Polybrominated diphenyl ethers (PBDEs), Metoxylated diphenyl ethers (MeO-PBDEs), and polychlorinated naphtalenes (PCNs) were extracted from blubber tissue and analyzed by GC/MS. Polyfluoroalkyl substances (PFAS) were extracted from livers and analyzed by LC-MS/MS. Although restricted by the number of pooled samples, survey points, and species available from the specimen banks, the results showed some interesting contamination patterns. Overall, pollutant concentrations showed signs of declining or levelling out, indicating a decrease in POP exposure in the studied areas in recent years. However, increasing levels of long-chain fluorinated compounds (PFCAs) present in most species is a finding of concern, and implies that a continuous monitoring of these compounds is important. Interestingly, a shift over time in the relative abundance of PFOS isomers in ringed seals was observed, indicating a change in exposure to PFOS in recent years. In many of the investigated species the MeO-PBDE levels equalled or exceeded the levels of PBDEs, showing that MeO-PBDEs can be major contributors to the organobromine load in marine mammal species. No apparent relation was found between PBDE and MeO-PBDE levels, adding further support for a natural origin of MeO-PBDEs.
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| 5. |
- Jörundsdóttir, Hrönn, 1978-
(author)
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Temporal and spatial trends of organohalogens in guillemot (Uria aalge) from North Western Europe
- 2009
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Doctoral thesis (other academic/artistic)abstract
- The Arctic and sub-Arctic region of the North Atlantic is a remote area, also in relations to environmental contaminants, such as POPs, BFRs and last but not least, PFCs. Both the BFRs and PFCs are considered emerging pollutants of significant environmental concern.The main objective of this thesis is to increase the knowledge and understanding of organohalogen compound distribution in the Nordic environment, their occurrence in biota and change over time. The temporal change of environmental contaminants in the Baltic Sea was monitored over the years 1971 to 2001, with emphasis on BCPS. Further, the pollution profile of the Nordic region was investigated by using common guillemot eggs. Further, to investigate a single remote site, Iceland, in more depth, eggs from seven marine bird species were collected and analysed. Both the organohalogen compounds mentioned above and their metabolites were investigated. The study focused also on an inter-species difference in the bird’s capability of metabolising xenobiotics.All environmental pollutants investigated in the Baltic Sea show decreasing levels over the time period investigated. BCPS showed a remarkably small change over time compared to other compounds. These results reinforce the previous findings, indicating the North Atlantic as remote where the concentrations of the organohalogens are lower compared to Europe in general. There are some exceptions however; the concentration of HCB is ubiquitously distributed across the study area. Further, the spatial trends of the PFCs are complicated and differ within the PFC group. When comparing bird species from Iceland, the concentration of organohalogens mainly depends on trophic level, while migration seems to contribute to a lesser extent. There are some similarities in the metabolism between the bird species investigated. However, the guillemot seems to distinguish itself from other marine birds, with a different composition of metabolites, indicating a different metabolic capacity.In conclusion, even human populations living in remote areas need to minimise the release of pollutants to the environment. Long term, well organised, and extensive governmental monitoring programs are highly recommended to follow the quality the environment and to detect any immediate and/or new threats of chemical pollutants.
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| 6. |
- Oesterle, Pierre, 1990-
(author)
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Exploring the fate of emerging contaminants during hydrothermal regeneration of carbonaceous adsorbents
- 2023
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Doctoral thesis (other academic/artistic)abstract
- Wastewater from households and industries commonly contain emerging contaminants that are not easily removed by most wastewater treatment plants. These contaminants can be removed through adsorption onto adsorbents, such as activated carbon or biochars. Previously, attention has been given to waste residues from the agriculture and forestry industry as potential raw materials for activated biochars, which could replace coal and coconut, common feedstocks for activated carbon production. This thesis investigates the factors governing the adsorption efficiencies of these activated biochars and explores the potential of hydrothermal regeneration as a post-treatment. The adsorption experiments showed that iron-doped (i.e., magnetic) activated biochar had two times more adsorption capacity than non-doped activated biochar (i.e., non-magnetic). However, the adsorption capacity of magnetic activated biochar was still inferior to activated carbon for removing sulfamethoxazole (8 mg/g vs. 42 mg/g) and caffeine (40 vs. 56 mg/g). Of the three conditions tested (i.e., salts, humic acids, and pH), only pH had a significant influence on the adsorption of the three selected contaminants onto activated biochars, and the biochars preferentially adsorbed neutral species. This observation is most likely explained by the π-π bonds. Hydrothermal regeneration effectively degraded trimethoprim, sulfamethoxazole, and caffeine at temperatures above 240 °C in the absence of adsorbent. Only trimethoprim generated transformation products that could be identified and quantified from non-targeted analysis. In presence of adsorbent, caffeine was not completely degraded at 280 or even 320 °C, suggesting that the activated biochars adsorb and to some extent shelter the contaminants from degradation.After hydrothermal regeneration, the activated biochars had an enhanced adsorption capacity for sulfamethoxazole, whereas lower adsorption capacity was observed for trimethoprim and caffeine. These changes in performance are believed to be related to the alteration of surface characteristics of activated biochar induced by the adsorbed contaminants during the hydrothermal reaction. Overall, the regeneration efficiency for the activated biochars was found to exceed 50 %. After three regeneration cycles, the regeneration efficiency was as high as 320 %. The results of this thesis suggest that activated biochars could remove emerging contaminants in water and hydrothermal regeneration could degrade most of the emerging contaminants, allowing the spent adsorbent to be reused.
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| 7. |
- Yin, Ge, 1987-
(author)
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Organohalogen contaminants in wildlife from the Yangtze River Delta : Development of methods and assessments of legacy and emerging persistent organic pollutants
- 2016
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Doctoral thesis (other academic/artistic)abstract
- Rapid economic development has occurred during the past few decades in China with the Yangtze River Delta (YRD) area as one of the most progressive areas. The urbanization, industrialization, agricultural and aquaculture activities result in extensive production and application of chemicals. Organohalogen contaminants (OHCs) have been widely used as i.e. pesticides, flame retardants and plasticizers. They are persistent, bioaccumulative and pose a potential threat to ecosystem and human health. However, limited research has been conducted in the YRD with respect to chemicals environmental exposure.The main objective of this thesis is to investigate the contamination level, distribution pattern and sources of OHCs in the YRD. Wildlife from different habitats are used to indicate the environmental pollution situation, and evaluate selected matrices for use in long term biomonitoring to determine the environmental stress the contamination may cause. In addition, a method is developed for dicofol analysis. Moreover, a specific effort is made to introduce statistic power analysis to assist in optimal sampling design.The thesis results show extensive contamination of OHCs in wildlife in the YRD. The occurrences of high concentrations of chlorinated paraffins (CPs) are reported in wildlife, in particular in terrestrial species, (i.e. short-tailed mamushi snake and peregrine falcon). Impurities and byproducts of pentachlorophenol products, i.e. polychlorinated diphenyl ethers (PCDEs) and hydroxylated polychlorinated diphenyl ethers (OH-PCDEs) are identified and reported for the first time in eggs from black-crowned night heron and whiskered tern. High concentrations of octachlorodibenzo-p-dioxin (OCDD) are determined in these samples. The toxic equivalents (TEQs) of polychlorinated dibenzo-p-dioxin (PCDDs) and polychlorinated dibenzofurans (PCDFs) are at mean levels of 300 and 520 pg TEQ g-1lw (WHO2005 TEQ) in eggs from the two bird species, respectively. This is two orders of magnitude higher than European Union (EU) regulation limit in chicken eggs. Also, a novel pattern of polychlorinated biphenyls (PCBs) with octa- to decaCBs, contributing to as much as 20% of total PCBs therein, are reported in birds. The legacy POPs shows a common characteristic with relatively high level of organochlorine pesticides (i.e. DDT, hexacyclohexanes (HCHs) and Mirex), indicating historic applications. In contrast, rather low concentrations are shown of industrial chemicals such as PCBs and polybrominated diphenyl ethers (PBDEs).A refined and improved analytical method is developed to separate dicofol from its major decomposition compound, 4,4’-dichlorobenzophenone. Hence dicofol is possible to assess as such. Statistic power analysis demonstrates that sampling of sedentary species should be consistently spread over a larger area to monitor temporal trends of contaminants in a robust manner.The results presented in this thesis show high CPs and OCDD concentrations in wildlife. The levels and patterns of OHCs in YRD differ from other well studied areas of the world. This is likely due to the extensive production and use of chemicals in the YRD. The results strongly signal the need of research biomonitoring programs that meet the current situation of the YRD. Such programs will contribute to the management of chemicals and environment in YRD, with the potential to grow into the human health sector, and to expand to China as a whole.
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| 8. |
- Cucarella Cabañas, Victor
(author)
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Recycling Filter Substrates used for Phosphorus Removal from Wastewater as Soil Amendments
- 2009
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Doctoral thesis (other academic/artistic)abstract
- This thesis studied the viability of recycling filter substrates as soil amendments after being used in on-site systems for phosphorus (P) removal from wastewater. Focus was put on the materials Filtra P and Polonite, which are commercial products used in compact filters in Sweden. A prerequisite for this choice was to review filter materials and P sorption capacity. The filter substrates (Filtra P, Polonite and wollastonite tailings) were recycled from laboratory infiltration columns as soil amendments to a neutral agricultural soil and to an acid meadow soil to study their impacts on soil properties and yield of barley and ryegrass. The amendments tended to improve the yield and showed a liming effect, significantly increasing soil pH and the availability of P. In another experiment, samples of Filtra P and Polonite were equilibrated in batch experiments with the two soils in order to study the P dynamics in the soil-substrate system. Batch equilibrations confirmed the liming potential of Filtra P and Polonite and showed that improved P availability in soils was strongly dependent on substrate P concentration, phase of sorbed P, and soil type. Finally, samples of Polonite used for household wastewater treatment were recycled as soil amendments to a mountain meadow and to an agricultural field for wheat cropping. The liming effect of Polonite was confirmed under field conditions and the results were similar to those of lime for the mountain meadow soil. However, the results were quite different for the agricultural field, where Polonite did not affect soil pH or any other chemical and physical soil properties investigated and had no impact on wheat yield and quality. The results from field experiments suggested that Polonite can be safely recycled to meadows and cropping fields at rates of 5-10 ton ha-1 but long-term studies are needed to forecast the effects of accumulation.
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| 9. |
- Arellano, Santiago, 1981
(author)
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Studies of Volcanic Plumes with Remote Spectroscopic Sensing Techniques -DOAS and FTIR measurements on volcanoes of the Network for Observation of Volcanic and Atmospheric Change-
- 2014
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Doctoral thesis (other academic/artistic)abstract
- Volcanism is a rich geodynamical process, closely linked to the origin and ongoing evolution of the lithosphere, atmosphere, hydrosphere and biosphere. Humans have benefited from the resources provided by volcanoes but also been threatened by the dangers of volcanic eruptions, which accurate prediction remains elusive. This is partly due to the inherent complexity of volcanic systems and partly because of the difficulty of conducting key observations to characterize them. In particular, since the segregation and escape of magmatic volatiles are essential mechanisms behind volcanic eruptions, monitoring the intensity and composition of the resulting emissions in the atmosphere is essential to characterize the state of volcanic activity; however, their direct measurement is not always feasible.Remote spectroscopic sensing, whereby gas species can be quantified by their spectral signatures in electromagnetic radiation gathered at a prudent distance from the plume, offers the possibility to conduct reliable and sustainable monitoring of volcanic emissions. To expand the remote sensing capabilities of volcanological observatories the Network for Observation of Volcanic and Atmospheric Change (NOVAC) was established in 2005. The central theme of this thesis is the acquisition, analysis and interpretation of measurements of volcanic gas emissions on volcanoes of NOVAC. Measurements of the mass flow rate of SO2 and the molar ratios of SO2 against BrO and HCl were obtained by scanning-Differential Optical Absorption Spectroscopy (DOAS) of scattered solar ultraviolet radiation and by Fourier-Transform Spectroscopy (FTIR) of direct solar infrared radiation. The uncertainty of the measurements is characterized and methods for combining observations from different sensors implemented. Statistical and physical models of degassing are proposed for selected volcanoes of the network. The resulting time-series of emission on 16 volcanoes is one of the more detailed compilations of volcanic degassing in the last decade, particularly from passive emissions which are difficult to detect from satellite platforms. This work aims at advancing our knowledge of volcanic eruptions for a better mitigation of their risks.
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| 10. |
- Luong, N. Tan, 1995-
(author)
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Water film-mediated mineralogical transformations and photocatalytic reactions
- 2023
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Doctoral thesis (other academic/artistic)abstract
- Mineral particles capture water vapor in the atmosphere in the form of water films that are only few monolayers thick. Water films form nanoscale hydration environments that mediate a wide range of important reactions in nature and technology. This thesis explored two important phenomena that commonly occur within the confines of water films: mineralogical transformations (Topic 1) and photocatalytic decomposition of organics (Topic 2). These transformations were chiefly identified by vibrational spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and (Transmission and Scanning) electron microscopy. Interpretations of reaction mechanisms were partially supported by chemometrics, kinetic and thermodynamic modeling, as well as molecular simulations.Mineralogical transformations (Topic 1) resolved in this thesis involved the hydroxylation (Papers I, II) and carbonation (Paper III) of periclase (MgO), and the oxidation of rhodochrosite (MnCO3) (Paper IV). Two types of MgO nanocubes with contrasting physical properties were used to resolve nucleation- and diffusion-limited hydroxylation reactions to brucite and carbonation reactions to amorphous magnesium carbonate (AMC). While nucleation-limited reactions completely transformed (8 nm) small and aggregated MgO nanocubes to brucite, the reactions became diffusion-limited in larger (32 nm) monodispersed MgO nanocubes because of brucite surface nanocoatings (Paper I). Additionally, brucite nanosheets grew under (GPa-level) crystallization pressures because of the important volumetric expansion of the reaction, which took place in a complex network of microporosity between the small and within the larger MgO nanocubes. Brucite stacking mechanisms, explored in Paper II, focused on the early stages of MgO-water interaction in water films of different thicknesses. These were suggested to involve the stacking and (epitaxial-like) growth of precursor Mg(OH)2 nanosheets in water films. Carbonation reactions explored in Paper III completely hampered hydroxylation reactions studied in Papers I and II, and produced AMC nanocoatings grown over an unreacted MgO core. Finally, oxidation-driven reactions involving rhodochrosite in Paper IV produced MnO2, Mn3O4, and MnOOH nanocoatings with growth rates being scaled with water loadings.Photocatalytic decomposition reactions of organics (Topic 2) were focused on the case of oxalate bound to TiO2 nanoparticles (Paper V). Photodecomposition rates scaled with humidity in oxygenated water films, and were explained by the combination of hole transfer (HT), ligand-to-metal charge transfer (LMCT), and the formation of hydroxyl radicals and reactive oxygen species. Decreasing rates in oxygen-free water films were, on the other hand, explained by water-driven charge localization, which eventually limited radical production and charge transfers via HT and LMCT. The reactions involved limited HT and LMCT processes which also competed with a charge recombination process across all humidity ranges.This thesis provides new insight into two key types of transformations mediated by water films on minerals. This knowledge can be used to understand the reactivity of mineral (nano)particles exposed to variations in atmospheric humidity and oxygen content, which are both highly relevant to a wide range of settings in nature and technology. It can also advance new ideas in the study of mineral growth, especially within the confines of nanometer-thick water films.
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