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.

In April 2010, approximately 4.9 million barrels of oil were accidentally released into the Gulf of Mexico during the Deepwater Horizon Macondo Mc252 Oil Spill. Some of the surface oil was carried by prevailing winds and currents and reached the coast of Louisiana impacting marsh and marine ecosystems. One and a half years after this incident, a set of oiled marsh samples (2 grab samples) coupled with nearby subtidal and intertidal cores (12 cores) were collected from Barataria Bay, Louisiana to determine the probable source of petroleum residues present and to characterize the chemical composition of the oil. Plus, pre-spill core which was collected from Barataria Bay in 2007 was analyzed to identify the background hydrocarbon composition of the area. Polycyclic aromatic hydrocarbons (PAH), total petroleum hydrocarbons (TPH), biomarker, and stable carbon isotope compositions of selected samples were detected using a GC-MS and an elemental analyzer Conflo system coupled to a DeltaPlusXP isotope ratio mass spectrometer. The comprehensive chemical data allowed us to classify the pre and post-spill samples into 4 Groups. According to this classification, Group 1 and Group 2 samples had the highest concentrations of petroleum-derived hydrocarbons. Group 3 and background samples, on the other hand, was dominated by biogenic signatures. Although a direct connection between the detected and spilled Macondo oils results are complicated due to confounding factors (e.g., already present hydrocarbons and weathering processes), our biomarker data indicates that both oils have similar signatures. This close genetic relationship was also identified by stable carbon isotope analysis. The impact of the Macondo Mc252 Oil Spill in Barataria Bay appears to be limited to areas closer to the source. The oil has undergone moderate weathering and has penetrated into, the at least, the top 9 cm sediments. Additionally, to examine the decadal-scale history of sedimentation in these marshes, a sediment core was analyzed for the radioisotope 137Cs. The observed sedimentation rate of 0.39 cm/yr shows that oil pollutant input into Barataria Bay has been ongoing for at least 50-60 years.

The seasonal pattern of the carbon isotope content (delta C-13) of atmospheric CO2 depends on local and nonlocal land-atmosphere exchange and atmospheric transport. Previous studies suggested that the delta C-13 of the net land-atmosphere CO2 flux (delta(source)) varies seasonally as stomatal conductance of plants responds to vapor pressure deficit of air (VPD). We studied the variation of (source) at seven sites across the United States representing forests, grasslands, and an urban center. Using a two-part mixing model, we calculated the seasonal delta(source) for each site after removing background influence and, when possible, removing delta C-13 variation of nonlocal sources. Compared to previous analyses, we found a reduced seasonal (March-September) variation in delta(source) at the forest sites (0.5 parts per thousand variation). We did not find a consistent seasonal relationship between VPD and delta(source) across forest (or other) sites, providing evidence that stomatal response to VPD was not the cause of the global, coherent seasonal pattern in (source). In contrast to the forest sites, grassland and urban sites had a larger seasonal variation in (source) (5) dominated by seasonal transitions in C-3/C-4 grass productivity and in fossil fuel emissions, respectively. Our findings were sensitive to the location used to account for atmospheric background variation within the mixing model method that determined (source). Special consideration should be given to background location depending on whether the intent is to understand site level dynamics or regional scale impacts of land-atmosphere exchange. The seasonal amplitude in delta C-13 of land-atmosphere CO2 exchange (delta(source)) varied across land cover types and was not driven by seasonal changes in vapor pressure deficit. The largest seasonal amplitudes of delta(source) were at grassland and urban sites, driven by changes in C-3/C-4 grass productivity and fossil fuel emissions, respectively. Mixing model approaches may incorrectly calculate delta(source) when background atmospheric observations are remote and/or prone to anthropogenic influence.

Dissolved organic matter (DOM) is a complex mixture of organic compounds and represents the largest reservoirs of carbon (C) on earth. Particulate organic matter (POM) is another important carbon component in C cycling and controls a variety of biogeochemical processes. Estuaries, as important interfaces between land and ocean, play important roles in retaining and transforming such organic matter (OM) and serve as both sources and sinks of DOM and POM. There is a diverse array of both autochthonous and allochthonous OM sources in wetland/estuarine ecosystems. A comprehensive study on the sources, transformation and fate of OM in such ecosystems is essential in advancing our understanding of C cycling and better constraining the global C budget. In this work, DOM characteristics were investigated in different estuaries. Dissolved organic matter source strengths and dynamics were assessed in a seagrass-dominated subtropical estuarine lagoon. DOM dynamics controlled by hydrology and seagrass primary productivity were confirmed, and the primary source of DOM was quantified using the combination of excitation emission matrix fluorescence with parallel factor analysis (EEM-PARAFAC) and stable C isotope analysis. Seagrass can contribute up to 72% of the DOM in the study area. The spatial and temporal variation of DOM dynamics was also studied in a freshwated dominated estuary fringed with extensive salt marshes. The data showed that DOM was primarily derived from freshwater marshes and controlled by hydrology while salt marsh plants play a significant role in structuring the distribution patterns of DOM quality and quantity. The OM dynamics was also investigated in a mangrove-dominate estuary and a comparative study was conducted between the DOM and POM pools. The results revealed both similarity and dissimilarity in DOM and POM composition. The dynamics of both OM pools are largely uncoupled as a result of source differences. Fringe mangrove swamps are suggested to export similar amounts of DOM and POM and should be considered as an important source in coastal C budgets. Lastly, chemical characterizations were conducted on the featured fluorescence component in OM in an attempt to better understand the composition and origins of the specific PARAFAC component. The traditionally defined ‘protein-like’ fluorescence was found to contain both proteinaceous and phenolic compounds, suggesting that the application of this parameter as a proxy for amino acid content and bioavailability may be limited.

Current Central American agricultural practices are environmentally and economically unsustainable, yet the ancient Maya who lived in the same region thrived for thousands of years. Archaeologists have attempted to understand the factors enabling the prolonged success and ultimate collapse of the Maya societies. Some have proposed that the karst seasonal wetlands, called bajos, that border many Maya sites in the region were an influential factor in the Maya's ability to flourish. For the past decade, researchers have used carbon isotope analyses to identify areas of ancient maize agriculture at Maya archaeological sites. In this study, we collected soil samples from bajos and upland areas at Tikal, one of the most prominent Maya sites, located in northern Guatemala, and analyzed the samples for evidence of past C4 vegetation. Our results confirm that bajos were utilized by the ancient Maya for long-term maize cultivation. Additionally, they suggest that modern agricultural methods in Guatemala that strategically utilize bajos may improve productivity and sustainability.

The objective of this study was to use soil chemical properties, particularly carbon isotopes to describe the agricultural landscape in the Blue Creek region on the Rio Bravo Escarpment in northwestern Belize. The primary question associated with this study focused on the comparative agricultural potential of the soils between the upland karst environment and the lowland coastal plains using the distribution and frequency of ancient Maya maize production. Soil physical features, such as clay concentrations throughout profiles in conjunction with soil chemical properties were used to aid in determining the level of ancient maize production. Isotopic evidence suggests that anciently, lowland soils were used for maize production more so than upland soils. In addition, profiles at Crocodile Lake indicate the potential for transport of soil δ13C signatures as a result of mass movement events.

The ancient inhabitants of the Maya Lowlands enjoyed a long and fruitful period of growth which climaxed at around AD 800. At that time, millions of people successfully subsisted in a challenging environment that today only supports a population a fraction of that size. These facts, and the subsequent "Maya Collapse", are the impetus of many recent studies that utilize environmental data, in addition to conventional archaeology, to investigate this Maya mystery. Pedological studies and stable carbon isotope analysis of soil organic matter, combined with Geographic Information Systems (GIS) are three tools that can be used to answer crucial questions as to how the Maya managed their soil resources. GIS maps that indicated areas of best agricultural potential based on slope and soil type were used as a guide to opportunistically sample soils in an area south of Piedras Negras Guatemala – an area that was densely vegetated and unexplored. Soils that represented the different soil resources of the area were sampled with a bucket auger at 15 cm intervals. The samples were then tested in a laboratory for physical and chemical characteristics and δ-13C values were determined for soil organic matter. Soil taxonomical descriptions indicated that overall the soil resources of the area were very good as almost all the soils were classified as Mollisols - the most fertile of all the soil orders. The suite of great groups found was Haprendolls, Argiudolls, Argiaquolls and Udorthents. The characteristics which distinguish these great groups were used to further investigate relative agricultural productivity from an ancient soil resources point of view. Haprendolls were better drained and probably made for good agricultural soils given soil depth and rainfall were adequate. The Argiudolls and especially the Argiaquolls were probably less favored because of very high clay contents that made them more difficult to work with and poor drainage. Stable carbon isotope analyses revealed strong evidence for maize agriculture in some environments of the study area. δ-13C values as high as -16.6‰ (76% C4—Carbon) were observed in areas of significant soil accumulation in well drained and moderately drained soils. Minimal evidence of maize agriculture was found in more marginal environments such as those with little soil accumulation or poorly drained areas. Also, the pattern of the graph of δ-13C values versus depth indicated that ancient agriculture occurred continuously in some areas, but in other areas as distinguishable events. Finally, when the strength of the C4 signal was represented graphically and overlaid with a modified GIS agricultural potential map, a visual representation of the extent and degree of ancient agriculture was achieved. Our findings suggest that upland agriculture was favored by the ancient Maya of Piedras Negras and that the region between Piedras Negras and Yaxchilan was an agriculturally important breadbasket. The methods and results of this study provide foundational information for the investigation of ancient Maya agriculture. In future studies, it may be possible to more systematically map ancient agricultural fields and estimate the carrying capacity of a region based on its soil resources.

The objective of this study was to use pedological evidence in conjunction with Geographic Information Systems, and soil physical and chemical analyses as means to better understand the agricultural landscape surrounding the ancient Maya city of Uci. Specifically, the query of this thesis is to determine whether there is an association between settlement density and soil resources, and what relationship if any there is between the ancient sacbe of Uci and its surrounding agricultural potential. Stable carbon isotope analysis of the humin fraction of the soil organic matter was conducted on several profiles from karst depressions known as rejolladas near the site center, and from a select number of sufficiently deep profiles along and surrounding the ancient sacbe, and from beneath ancient structures. A strong C isotopic signature of ancient C4 crops was found in a limited number of profiles while a majority of the profiles showed no evidence, or little to inconclusive evidence due to a mixture of C3 and C4 plants in the natural landscape. A majority of the soils surrounding Uci are shallow to extremely shallow and many profiles sampled and studied did not allow for C isotopic analysis. Isotopic evidence along with other soil chemical and physical characteristics suggests that settlement density was linked to soil resources, specifically in the case of the rejolladas proximity to the Uci site center. However, it does not appear that the construction and location of the sacbe was linked to its surrounding soil resources or agricultural potential even though ancient maize crops may have been cultivated sporadically close to the sacbe and nearby structures. The soil resources of Uci are not conducive to the production of large maize crops and the ancient Maya of this area likely utilized maize along with alternative crops, arboriculture, wild game and trade to sustain its population.

Late Mississippian, Mauch Chunk Group strata constitute a westward-thinning clastic wedge of strata up to 1000m thick that developed in the Central Appalachian Basin over a ~ 7 million year time interval. Included within the Mauch Chunk Group are multiple incised-valley fills and a distinctive prodeltaic succession of laminated sandstones and mudstones. Calculated estimates of drainage basin areas for incised-valley fills in the Mauch Chunk Group range from > 1,000,000 km2 for the Stony Gap Sandstone to < 100,000 km2 for the Princeton Formation. Drainage area estimates are consistent with detrital zircon geochronology and petrographic data and suggest that the Stony Gap and Ravencliff incised-valley fills were derived from distal, northern and northwestern cratonic sources that dispersed sediment into NE-SW-oriented, longitudinal incised-valley drainages and that the Princeton Formation was derived from proximal tectonic highland sources along the eastern margin of the Appalachian Basin which dispersed sediment into a transverse incised-valley. The Pride Shale overlies the Princeton incised valley fill and records a hierarchy of tidal periodicities is preserved in the Pride Shale. Microlaminated, semi-diurnal sandstone-siltstone/shale couplets record the dominant ebb tide of the day. Up to 17 semi-diurnal couplets are stacked into neap-spring (fortnightly) tidal cycles. Neap-spring cycles are arranged in thickening and thinning that record seasonal cycles driven by the annual monsoon. Total organic carbon (TOC) values are a proxy for annual climatic cycles. TOC contents are higher within intermonsoonal and lower within monsoonal components of annual cycles reflecting, respectively, lesser and greater dilution by terrestrial flux. / Master of Science

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