<p>The objective of this thesis is to improve the understanding of what processes and mechanism affects the distribution of polychlorinated biphenyls (PCBs) and organic carbon in coastal sediments. Because of the strong association of hydrophobic organic contaminants (HOCs) such as PCBs with organic matter in the aquatic environment, these two entities are naturally linked. The coastal environment is the most complex and dynamic part of the ocean when it comes to both cycling of organic matter and HOCs. This environment is characterised by the largest fluxes and most diverse sources of both entities. A wide array of methods was used to study these processes throughout this thesis. In the field sites in the Stockholm archipelago of the Baltic proper, bottom sediments and settling particulate matter were retrieved using sediment coring devices and sediment traps from morphometrically and seismically well-characterized locations. In the laboratory, the samples have been analysed for PCBs, stable carbon isotope ratios, carbon-nitrogen atom ratios as well as standard sediment properties. From the fieldwork in the Stockholm Archipelago and the following laboratory work it was concluded that the inner Stockholm archipelago has a low (≈ 4%) trapping efficiency for freshwater-derived organic carbon. The corollary is a large potential for long-range waterborne transport of OC and OC-associated nutrients and hydrophobic organic pollutants from urban Stockholm to more pristine offshore Baltic Sea ecosystems.</p><p>Theoretical work has been carried out using Geographical Information Systems (GIS) and statistical methods on a database of 4214 individual sediment samples, each with reported individual PCB congener concentrations. From this work it was concluded that the continental shelf sediments are key global inventories and ultimate sinks of PCBs. Depending on congener, 10-80% of the cumulative historical emissions to the environment are accounted for in continental shelf sediments. Further it was concluded that the many infamous and highly contaminated surface sediments of urban harbours and estuaries of contaminated rivers cannot be of importance as a secondary source to sustain the concentrations observed in remote sediments. Of the global shelf PCB inventory < 1% are in sediments near population centres while ≥ 90% is in remote areas (> 10 km from any dwellings). The remote sub-basin of the North Atlantic Ocean contains approximately half of the global shelf sediment inventory for most of the PCBs studied.</p>

Although studies on stable-carbon isotopes in trees from temperate zones provide abundant paleoclimatic data, tropical trees are still understudied in this context. Therefore this study examined the variability of intra- and inter-annual stable-carbon isotopic pattern in several tree species from various tropical climates. The 𝛿¹³C values of samples of 12 broadleaved trees (seven species) from various paleotropical and neotropical sites along a climatic moisture gradient were investigated. The inter-annual variability between species and sites was studied. Further the relationship between 𝛿¹³C and precipitation time series was analyzed. Results show that tropical tree species show a similar variability in carbon isotopic composition as temperate tree species. Significant correlations between annual precipitation and tree-ring 𝛿¹³C time series were negative. Successful crossdating of a tree-ring 𝛿¹³C time series highlights the potential of carbon isotope measurements for tropical tree-ring analytical studies. Tropical broadleaved trees are able to capture a carbon isotopic signal in their annual rings even under everwet conditions and show good potential for paleoclimatic research.

The purpose of this study was to use soil physical and chemical analyses to better understand the ancient agricultural landscape around the ancient Maya cities of Rio Amarillo and Piedras Negras, two tributary sites to Copan, Honduras. Our primary objective was to determine whether a mass erosion event around 800 A.D. occurred which could have caused crop failure and famine or if stable soil conditions persisted during the collapse of these city-states. Stable carbon isotope analysis of the humin fraction of the soils showed that much of this valley was used anciently for agriculture, including hillslopes and hilltops; however, there is no evidence of mass erosion in the soil profiles. Soil horizon development and texture is consistent with stable soil conditions in this area. The demise of these city-states was likely caused by a variety of factors including warfare and political unrest, and not solely by environmental degradation as postulated in previous studies of the valley.

Stable carbon isotope analyses of the humin fraction of the soil organic matter were conducted on more than 160 soil profiles from Tikal, Guatemala. The profiles were collected from near areas associated with the earthworks of Tikal; an ancient ditch and parapet construction hypothesized to have formed ancient boundaries of the polity. In addition to the isotope analyses, the physical and chemical characteristics of the horizons were determined. Maize, a C4 plant, formed an integral part of the ancient Maya diet and is the only known C4 plant cultivated by the Maya. Prior to and subsequent to the ancient Maya occupation of Tikal, the landscape was dominated by C3 forest vegetation. Over the centuries C4 plant biomass including rhizodeposition decomposed to form soil organic matter that contains a distinct C4 signature reflecting the vegetation history of the area. Forested areas anciently cleared for agriculture were identified through interpretation of significant isotopic shifts that signaled past vegetation changes. Buried horizons were encountered in the upland depressions and bajo wetlands. The aggraded soil deposits were likely the result of increased human activity related to settlement and agriculture. The buried horizons and the overlying sediments exhibited stable carbon isotope shifts associated with forest clearance and maize agriculture. Geospatial analysis of the stable carbon isotope ratios indicated that ancient Maya agriculture was focused on deeper footslope and toeslope soils in both bajos and upland depressions. Some evidence of infield agriculture or food processing was also encountered in connection with ancient settlement at upland locations. The soil data provide insight into ancient land use and sustainability that could potentially contribute to subsistence and population reconstruction models.

The chronostratigraphic correlation of the Silurian units in Iowa is complicated by complex carbonate depositional environments and poor biostratigraphic control. In this study, we integrate conodont biostratigraphic data with carbon isotope (δ 13Ccarb) chemostratigraphic data from the Blanding, Hopkinton, Scotch Grove, and LaPorte City formations of Iowa to provide a precise chronostratigraphic framework for regional and global correlation. Conodonts from the LaPorte City Formation of eastern Iowa (East-Central Iowa Basin) in the Garrison Core indicate an early to middle Telychian age for the formation. Conodonts diagnostic of the Pterospathodus eopennatus Superzone, Pterospathodus eopennatus ssp. nov. 2 Zone, and Pterospathodus amorphognathoides angulatus Zone were recovered, allowing for the first direct comparison of the stratigraphic ranges of conodont species from the North American Midcontinent and the Baltic basin. The morphology of Pseudolonchodina fluegeli ssp. n. Männik (2007) co-occurs with Pseudolonchodina fluegeli fluegeli sensu Männik (2007a) in the LaPorte City Formation and are not stratigraphically separated in Iowa as they are in the East Baltic. Wurmiella? polinclinata polinclinata ranges much lower in the East-Central Iowa Basin (Pt. eopennatus ssp. nov. 2 Zone) than the Baltic Basin, so it cannot be used as an index fossil diagnostic of the Pt. am. amorphognathoides Zone in global correlations. Three carbon isotope excursions were recovered from the Hopkinton and Scotch Grove formations. The late Aeronian (herein renamed “Farmers Creek”) carbon isotope excursion and a heretofore unrecorded carbon isotope excursion were recorded from the Hopkinton Formation in the SS-10 Core (Jones County). The Farmers Creek Excursion can be correlated to Johnson County, where it was recorded in the Hopkinton Formation by McAdams et al. (in prep). The Valgu excursion was recovered from the uppermost Hopkinton Formation through the overlying Buck Creek Quarry Member of the Scotch Grove Formation in the Garrison Core (Benton County). This excursion can be correlated to Johnson County, where it was recorded in the same formations. The integration of conodont biostratigraphic and carbon isotope chemostratigraphic data from the Silurian of Iowa allows for the first regional chronostratigraphic correlations at a resolution finer than stage level. The oxygen and carbon isotope values from the Garrison Core and the evidence for post-diagenetic karsting and fluid movement through the units may provide further evidence that the dolomitization process of the LaPorte City Formation was halted by the influx of meteoric phreatic water. This study shows the first high-resolution chronostratigraphic correlation of Silurian units in Iowa, and highlights the utility of integrated carbon isotope chemostratigraphy as a tool for chronostratigraphic correlation in strata with poor biostratigraphic control. The conodonts recovered from the LaPorte City Formation shows the utility of the small limestone formations on the northwest flank of the East-Central Iowa Basin for refining global Silurian conodont biostratigraphic zonation.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous, toxic contaminants that are released to the environment from various petrogenic and pyrogenic sources. In an effort to more clearly identify and trace sources of PAHs in the environment, purification and compound specific isotope analysis methods were developed to accurately measure the stable carbon isotope ratio of individual PAHs. Development of the method included improving accuracy and precision of the isotopic measurement by producing highly pure extracts using various chromatographic techniques. The method was refined by improving compound separations using purification techniques and high resolution chromatographic columns. The purification method consists of alumina/silica gel column chromatography, gel permeation chromatography and thin layer chromatography. The mean recovery of PAHs after the purification procedure was approximately 80 %. Sample purities after purification were verified by GC/FID and full scan mass spectrometry. To better resolve peaks and provide more accurate stable carbon isotope measurements, various gas chromatographic conditions were evaluated. The precision of the method ranged between 0.08 and 0.43 . The analytical protocols were evaluated to confirm compositional and stable isotopic integrity during purification and stable isotopic analysis. To confirm the utility of the purification and isotope analysis methods, various environmental samples from marine, land and lacustrine environments were analyzed. The isolates were analyzed for the composition and the stable carbon isotope ratios of PAHs. The stable carbon isotope ratio was measured by GC/IRMS and the results, along with quantitative compound compositions, were used to characterize and identify the contaminant sources. The sources of the PAHs in the study areas were differentiated by PAH molecular ratios and confirmed by stable carbon isotope ratios. This study confirms that compound specific isotope analysis of pollutants by GC/IRMS can be used to identify PAH sources in environmental samples. The study also confirms that the purification and stable carbon isotope analysis methods that were developed can be used to accurately measure the stable carbon isotope ratios of PAHs in environmental samples for the purpose of source identification. GC/IRMS measurement of stable isotopic compositions can be an effective fingerprinting method when used in conjunction with traditional molecular composition methods.

The objective of this thesis is to improve the understanding of what processes and mechanism affects the distribution of polychlorinated biphenyls (PCBs) and organic carbon in coastal sediments. Because of the strong association of hydrophobic organic contaminants (HOCs) such as PCBs with organic matter in the aquatic environment, these two entities are naturally linked. The coastal environment is the most complex and dynamic part of the ocean when it comes to both cycling of organic matter and HOCs. This environment is characterised by the largest fluxes and most diverse sources of both entities. A wide array of methods was used to study these processes throughout this thesis. In the field sites in the Stockholm archipelago of the Baltic proper, bottom sediments and settling particulate matter were retrieved using sediment coring devices and sediment traps from morphometrically and seismically well-characterized locations. In the laboratory, the samples have been analysed for PCBs, stable carbon isotope ratios, carbon-nitrogen atom ratios as well as standard sediment properties. From the fieldwork in the Stockholm Archipelago and the following laboratory work it was concluded that the inner Stockholm archipelago has a low (≈ 4%) trapping efficiency for freshwater-derived organic carbon. The corollary is a large potential for long-range waterborne transport of OC and OC-associated nutrients and hydrophobic organic pollutants from urban Stockholm to more pristine offshore Baltic Sea ecosystems. Theoretical work has been carried out using Geographical Information Systems (GIS) and statistical methods on a database of 4214 individual sediment samples, each with reported individual PCB congener concentrations. From this work it was concluded that the continental shelf sediments are key global inventories and ultimate sinks of PCBs. Depending on congener, 10-80% of the cumulative historical emissions to the environment are accounted for in continental shelf sediments. Further it was concluded that the many infamous and highly contaminated surface sediments of urban harbours and estuaries of contaminated rivers cannot be of importance as a secondary source to sustain the concentrations observed in remote sediments. Of the global shelf PCB inventory &lt; 1% are in sediments near population centres while ≥ 90% is in remote areas (&gt; 10 km from any dwellings). The remote sub-basin of the North Atlantic Ocean contains approximately half of the global shelf sediment inventory for most of the PCBs studied.

Speleothems are considered a reliable proxy for paleoclimatic reconstructions and analysis of stable carbon isotopes in speleothems is used for paleoclimatic reconstructions. However, in temperate areas that lacks C4 vegetation there are uncertainties in how to interpret changes in the δ13C signal. The aim of this study is toincrease the understanding of how the δ13C signal in speleothems from temperateareas can be interpreted. The study was divided in two parts, first a literature studythat focused on interpretations of the δ13C signal in speleothems from temperate areasand a case study in which a comparison of seven 13C records from similarenvironments in the Scandes Mountains and the Alps are made. The results from the literature study were used in the case study to draw conclusions on tree line and vegetation changes during Holocene in central northern Scandinavia. The study showed that trends in interpretation of the δ13C signal in speleothems from temperateareas are that low δ13C values are interpreted as wetter, warmer conditions with higherbio productivity, and high δ13C values are interpreted as colder, drier conditions withlower bio productivity. Further it was found in the study that vegetation changes seen in Holocene pollen data are also seen in δ13C records from Scandinavia. The δ13Csignal in temperate speleothems therefore appears to be related to changes invegetation density and to tree-line changes.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous, toxic contaminants that are released to the environment from various petrogenic and pyrogenic sources. In an effort to more clearly identify and trace sources of PAHs in the environment, purification and compound specific isotope analysis methods were developed to accurately measure the stable carbon isotope ratio of individual PAHs. Development of the method included improving accuracy and precision of the isotopic measurement by producing highly pure extracts using various chromatographic techniques. The method was refined by improving compound separations using purification techniques and high resolution chromatographic columns. The purification method consists of alumina/silica gel column chromatography, gel permeation chromatography and thin layer chromatography. The mean recovery of PAHs after the purification procedure was approximately 80 %. Sample purities after purification were verified by GC/FID and full scan mass spectrometry. To better resolve peaks and provide more accurate stable carbon isotope measurements, various gas chromatographic conditions were evaluated. The precision of the method ranged between 0.08 and 0.43 . The analytical protocols were evaluated to confirm compositional and stable isotopic integrity during purification and stable isotopic analysis. To confirm the utility of the purification and isotope analysis methods, various environmental samples from marine, land and lacustrine environments were analyzed. The isolates were analyzed for the composition and the stable carbon isotope ratios of PAHs. The stable carbon isotope ratio was measured by GC/IRMS and the results, along with quantitative compound compositions, were used to characterize and identify the contaminant sources. The sources of the PAHs in the study areas were differentiated by PAH molecular ratios and confirmed by stable carbon isotope ratios. This study confirms that compound specific isotope analysis of pollutants by GC/IRMS can be used to identify PAH sources in environmental samples. The study also confirms that the purification and stable carbon isotope analysis methods that were developed can be used to accurately measure the stable carbon isotope ratios of PAHs in environmental samples for the purpose of source identification. GC/IRMS measurement of stable isotopic compositions can be an effective fingerprinting method when used in conjunction with traditional molecular composition methods.

Stable carbon isotope ratios (δ13C) in tree-ring cellulose are modified by environmental conditions occurring during carbon fixation. Researchers have however not reached a consensus as to whether extractives, lignin and/or hemicelluloses, all with specific isotopic signatures, should be removed prior to dendroisotopic analysis. The topic of the first paper dealt with the comparison of Thuja occidentalis L. wood components and their suitability for subsequent dendroisotopic analyses. It was recommended that holocellulose be isolated since an alpha-cellulose yield may be too low for subsequent mass spectrometer analysis, especially when narrow rings are encountered and multiple stable isotope analyses are to be performed per sample. The second paper investigated the associations between the ring-width and δ13C chronologies with climate variables. The δ13C chronology spanned from 1650 to 2006 A.D. and incorporated dead and living T. occidentalis trees selected from two sites in central Manitoba, Canada. Compared to the δ13C values, ring width was more often associated with climate conditions in the year prior to ring formation. However, moisture stress was limiting for both radial growth and carbon assimilation. During the year of ring-formation, ring width was associated with spring and early summer conditions whereas, δ13C was more indicative of overall summer conditions. Nonetheless, each of ring width and δ13C contained individualistic climate information which could be used in tandem for long-term climate reconstruction.