Sampling methods for dentine and bone collagen have been evolving for several decades. Incremental dentine collagen sampling and bone collagen sampling have been limited by the available technology throughout that time. As the technology for isotope ratio mass spectrometry analysis improves, the sampling methods should improve as well. This research focused on developing a new incremental dentine collagen sampling method and bone collagen microsampling method for stable isotope analysis. This research aimed to increase the temporal resolution of incremental dentine collagen sampling and provided sequential collagen sampling from bone collagen for stable carbon and nitrogen isotope analysis while limiting the destructive nature of bioarchaeological analysis. It was determined that the temporal resolution for incremental analysis could be reduced to approximate three months, opposed to the nine months found in other sampling methods. It was also determined that detailed isotopic data could be obtained from bone collagen when sampling the microstructures. The increased amount of isotopic data from the bone collagen was an improvement on the commonly used bulk collagen sampling. This research can be utilised to answer several of the questions that archaeologists have been asking about past populations. Isotopic analysis using the methods developed in the research can provide a more detailed observation of the diet and health of past populations. In addition, the developed methods for bone and dentine collagen reduced the amount of tissue subjected to destructive analysis.

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Thesis (Ph. D.)--Joint Program in Oceanography (Massachusetts Institute of Technology, Dept. of Earth, Atmospheric, and Planetary Sciences; and the Woods Hole Oceanographic Institution), 1986. / Vita. / Includes bibliographical references (leaves 208-215). / A study of the remineralization of organic carbon was conducted in the organic-rich sediments of Buzzards Bay, MA. Major processes affecting the carbon chemistry in sediments are reflected by changes in the stable carbon isotope ratios of dissolved inorganic carbon (XCO2) in sediment pore water. Six cores were collected seasonally over a period of two years. The following species were measured in the pore waters: JC02, &'3 C-2CO2, P04, JH 2S, Alk, DOC, and Ca. Measurements of pore water collected seasonally show large gradients with depth, which are larger in summer than in winter. The 613C (PDB) of IC02 varies from 1.3 o/oo in the bottom water to approximately -10 o/oo at 30 cm. During all seasons, there was a trend towards more negative values with depth in the upper 8 cm due to the remineralization of organic matter. There was a trend toward more positive values below 8 cm, most likely due to biological irrigation of sediments with bottom water. Below 16-20 cm, a negative gradient was re-established which indicates a return to remineralization as the main process affecting pore water chemistry. Using the XC02 depth profile, it was estimated that 67-85 gC/m 2 are oxidized annually and 5 gC/m 2-yr are buried. The amount of carbon oxidized represented remineralization occurring within the sediments. This estimate indicated that approximately 20% of the annual primary productivity reached the sediments. The calculated remineralization rates varied seasonally with the high of 7.5 x 10-' mol/L-sec observed in August 84 and the low (0.6 x 10-) in December 83. The calculated remineralization rates were dependent on the amount of irrigation in the sediments; if the irrigation parameter is known to ±20%, then the remineralization rates are known to this certainty also. The amount of irrigation in the sediments was estimated using the results of a seasonal study of 2 2 2Rn/ 22 'Ra disequilibria at the same study site (Martin, 1985). Estimates of the annual remineralization in the sediments using solid-phase data indicated that the solid-phase profiles were not at steady-state concentrations. The isotopic signature of 2C02 was used as an indicator of the processes affecting IC02 in pore water. During every month, the oxidation of organic carbon to C02 provided over half of the carbon added to the IC02 pool. However, in every month, the 6'"C of XCO2 added to the pore water in the surface sediments was greater than -15 o/oo, significantly greater than the 613C of solid-phase organic carbon in the sediments (-20.6 o/oo). The 613C of IC02 added to the pore water in the sediments deeper than 7 cm was between -20 and -21 o/oo, similar to the organic carbon in the sediments. Possible explanations of the 1 3C-enrichment observed in the surface sediments were: a) significant dissolution of CaC0 3 (613C = +1.7 o/oo) b) the addition of significant amounts of carbonate ion from bottom water to pore water c) an isotopic difference between the carbon oxidized in the sediments and that remaining in the sediments. The effect of CaC0 3 dissolution was quantified using measured dissolved Ca profiles and was not large enough to explain the observed isotopic enrichment. An additional source of 13C-enriched carbon was bottom water carbonate ion. In every month studied, there was a net flux of 2C0 2 from pore water to bottom water. The flux of pore water 2C02 to bottom water ranged from a minimum of 10 x 10-12 mol/cm 2 -sec in December 83 to a maximum of 50 x 10-12 mol/cm2-sec in August 84. However, because the pH of bottom water was about 8 while that of the pore water was less than or equal to 7, the relative proportion of the different species of inorganic carbon (H2CO, HCO-, C0~) was very different in bottom water and pore water. Thus, while there was a net flux of IC0 2 from pore water to bottom water, there was a flux of carbonate ion from bottom water to pore water. Because bottom water JC02 was more 13C-enriched than pore water JC0 2, the transfer of bottom water carbonate ion to pore water was a source of 13C-enriched carbon to the pore water. If the &'3C of CO2 added to the pore water from the oxidation of organic carbon was -20.6 o/oo, then the flux of C3% from bottom water to pore water must have been 10-30% of the total flux of 2C02 from pore water to bottom water. This is consistent with the amount calculated from the observed gradient in carbonate ion. Laboratory experiments were conducted to determine whether the 613C of C02 produced from the oxidation of organic carbon (613C-OCOX) was different from the 613C of organic carbon in the sediments (613C-SOC). In the laboratory experiments, mud from the sampling site was incubated at a constant temperature. Three depths were studied (0-3, 10-15, and 20-25 cm). For the first study (IEl), sediment was stirred to homogenize it before packing into centrifuge tubes for incubation. For the second study (IE2), sediment was introduced directly into glass incubation tubes by subcoring. The second procedure greatly reduced disturbance to the sediment. Rates of C02 production were calculated from the concentrations of 2C02 measured over up to 46 days. In both studies, the values of Re in the deeper intervals were about 10% of the surface values. This was consistent with the field results, although the rates decreased more rapidly in the field. In all cases, the remineralization rates during the beginning of IEl were much greater than those at the beginning of IE2. The sediment for IEl was collected in February 84. The measured value of Rc in the surface sediment of the laboratory experiment (24 x 10- mol/L-sec) was much greater than the value of Rc observed in the field in another winter month, December 83 (.62 x 10~9). The sediment for IE2 was collected in August 85. The measured values of Re in the surface sediment (6.6-12 x 10~9 mol/L-sec) were consistent with the field values from August 84 (7.5 x 10-9). The XC02 results indicated that IE2 reproduced field conditions more accurately than IEl did. The isotopic results from the experiments strongly suggested that 613C-OCOX in the surface sediments (-17.8 o/oo ± 1.9 o/oo) was greater than 6'3C-SOC (-20.6 ± 0.2 o/oo). The magnitude of the observed fractionation was small enough that the observed values of 613C-C02 in the pore waters could be explained by fractionated oxidation coupled with the diffusion of carbonate ion from bottom water to pore water. The observed fractionation was most likely due to the multiple sources of organic carbon to coastal sediments. A study of the natural levels of radiocarbon in these sediments indicated that the carbon preserved in the sediments is approximately 30% terrestrial while the rest is from phytoplankton. / by Ann P. McNichol. / Ph.D.

This study investigated stable-isotope ratio evidence of weaning for the late Anglo-Saxon population of Raunds Furnells, Northamptonshire, UK. delta(15)N and delta(13)C values in rib collagen were obtained for individuals of different ages to assess the weaning age of infants within the population. A peak in delta(15) N values at about 2-year-old, followed by a decline in delta(15) N values until age three, indicates a change in diet at that age. This change in nitrogen isotope ratios corresponds with the mortality profile from the site, as well as with archaeological and documentary evidence on attitudes towards juveniles in the Anglo-Saxon period. The pattern of delta(13) C values was less clear. Comparison of the predicted age of weaning to published data from sites dating from the Iron Age to the 19th century in Britain reveals a pattern of changing weaning practices over time, with increasingly earlier commencement and shorter periods of complementary feeding in more recent periods. Such a change has implications for the interpretation of socioeconomic changes during this period of British history, since earlier weaning is associated with decreased birth spacing, and could thus have contributed to population growth.

Distinguishing animal fats from plant oils in archaeological residues is not straightforward. Characteristic plant sterols, such as beta-sitosterol, are often missing in archaeological samples and specific biomarkers do not exist for most plant fats. Identification is usually based on a range of characteristics such as fatty acid ratios, all of which indicate that a plant oil may be present, none of which uniquely distinguish plant oils from other fats. Degradation and dissolution during burial alter fatty acid ratios and remove short-chain fatty acids, resulting in degraded plant oils with similar fatty acid profiles to other degraded fats. Compound-specific stable isotope analysis of delta(13)C(18:0) and delta(13)C(16:0), carried out by gas chromatography/combustion/isotope ratio mass spectrometry (GC/C/IRMS), has provided a means of distinguishing fish oils, dairy fats, ruminant and non-ruminant adipose fats, but plant oils are rarely included in these analyses. For modern plant oils where C(18:1) is abundant, delta(13)C(18:1) and delta(13)C(16:0) are usually measured. These results cannot be compared with archaeological data or data from other modern reference fats where delta(13)C(18:0) and delta(13)C(16:0) are measured, as C(18:0) and C(18:1) are formed by different processes resulting in different isotopic values. Eight samples of six modern plant oils were saponified, releasing sufficient C(18:0) to measure the isotopic values, which were plotted against delta(13)C(16:0). The isotopic values for these oils, with one exception, formed a tight cluster between ruminant and non-ruminant animal fats. This result complicates the interpretation of mixed fatty residues in geographical areas where both animal fats and plant oils were in use.

Among the most compelling and least well-understood tree species growing in the temperate forests of southern South America is Fitzroya cupressoides, a high biomass species and the second longest-lived tree species in the world. This thesis quantified the main components of the carbon cycle in Fitzroya forests (i.e. net primary productivity (NPP) and soil respiration) and evaluated the environmental variables that are most related to them. The study was focused on medium-age and old-growth forests growing in the Coastal Range (Alerce Costero National Park, AC) and the Andean Cordillera (Alerce Andino National Park, AA) of southern Chile, respectively. The specific objectives of this thesis were to: 1) assess the forest structure, species composition and characterise the environmental conditions of these forests; 2) assess biomass, aboveground NPP, carbon allocation and mean wood residence time in these forests; 3) assess soil respiration and relate it to soil environmental conditions. Additionally, to use a mass balance approach to estimate fine root productivity; 4) estimate total NPP using biometric and indirect estimates of productivity; 5) evaluate the climatic factors mainly related to Fitzroya stem radial change on an intra-annual basis; and 6) evaluate changes in Fitzroya's tree growth and carbon isotopes during recent decades, and determine which environmental factors are more related to them. The last two objectives focus on Fitzroya as the dominant species and the subject of this study. Two 0.6 ha plots were installed within each national park; NPP was estimated for a year and soil respiration and high resolution stem growth measurements were monitored over almost two years. Aboveground biomass estimates for the Andean site are among the most massive reported in the world and carbon fluxes in Fitzroya forests are among the lowest reported for temperate wet forests worldwide. The longevity as well as the particularly rainy and nutrient poor soil conditions where these ecosystems grow may influence their exceptionally slow carbon dynamics. Differences in carbon fluxes between sites seem most probably driven by different environmental conditions rather than by developmental stage. Moreover, carbon fluxes were more sensitive to interannual climate variability in AC than AA. Warmer and drier summer conditions, likely to become more common under future climate change, more significantly affected stem growth and soil respiration in the Coastal Range than in the Andes. Regarding long-term changes, tree growth has been decreasing in the coastal site in the last 40 years and increasing in the Andes since the 1900s. These trends have been accompanied by an increase in intrinsic water use efficiency which is likely caused by rises in CO₂ and changes in climate conditions in both sites. Although Fitzroya grows in particularly wet and cool areas, projected drier and warmer conditions may have a negative effect on Fitzroya stem growth and carbon sequestration in both study sites. This effect would be more critical in the Coastal Range though, because of its more Mediterranean climate influence and more restrictive soil conditions in this area. Adequate resources are needed for the monitoring and conservation of these slow growth and massive forests especially in the Coastal Range, in order to avoid ongoing illegal cuttings and threatening forest fires.

Permafrost soils in the Arctic store large quantities of organic matter, roughly twice the amount of carbon that was present in the atmosphere before the industrial revolution. This freeze-locked carbon pool is susceptible to thawing caused by amplified global warming at high latitudes. The remobilization of old permafrost carbon facilitates its degradation to carbon dioxide and methane, thereby providing a positive feedback to climate change. Accelerating coastal erosion in addition to projected rising river discharge with enhancing sediment loads are anticipated to transport increasing amounts of land-derived organic carbon (OC) to the Arctic Ocean. On its shallow continental shelves, this material may be remineralized in the water column or in the sediments, transported without being altered off shelf towards the deep sea of the Arctic Interior or buried in marine sediments and hence sequestered from the contemporary carbon cycle. The fate of terrigenous material in the marine environment, though offering potentially important mechanisms to either strengthen or attenuate the permafrost-carbon climate feedback, is so far insufficiently understood. In this doctoral thesis, sediments from the wide East Siberian Arctic Shelf, the world’s largest shelf-sea system, were used to investigate some of the key processes for OC cycling. A range of bulk sediment properties, carbon isotopes and molecular markers were employed to elucidate the relative importance of different organic matter sources, the role of cross-shelf transport and the relevance of degradation during transport and after burial. Overall, OC released from thawing permafrost constitutes a significant proportion of the sedimentary organic matter on the East Siberian Arctic Shelf. Two sediment cores from the inner and outer East Siberian Sea recorded no substantial changes in source material or clear trends in degradation status for the last century. With increasing distance from the coast, however, strong gradients were detected towards lower concentrations of increasingly reworked land-derived OC. The time spent during cross-shelf transport was consequently found to exert first-order control on degradation. Compound-specific radiocarbon dating on terrigenous biomarkers revealed a net transport time of ~4 000 years across the 600 km wide Laptev Sea shelf, yielding degradation rate constants for bulk terrigenous OC and specific biomarkers on the order of 2-4 kyr-1. From these results, the carbon flux released by degradation of terrigenous OC in surface sediments was estimated to be ~1.7 Gg yr-1, several orders of magnitude lower than what had been quantified earlier for dissolved and particulate OC in the water column. Lower oxygen availability and close associations with the mineral matrix may protect sedimentary OC from remineralization and thereby weaken the permafrost-carbon feedback to present climate change. / <p>At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Submitted. Paper 4: Manuscript.</p>

Growth rates, δ18O and δ13C of five stalagmites from the west coasts of North and South Islands, New Zealand, provide records of millennial-scale climate variability over the last ~75 kyr. Thirty-five uranium-series ages were used to provide the chronology. δ18O of stalagmite calcite was influenced by changes in moisture source region, temperature and both δ18O and δ13C primarily display a negative relationship with rainfall. To assist interpretation of climatic signals δ18O profiles were adjusted for the ice-volume effect. Changes in these proxies reflect changes in the strength of the circumpolar westerly circulation and the frequency of southwesterly flow across New Zealand. MIS 4 was a period of wet and cool climate lasting from 67.7 to 61.3 kyr B.P., expressed in the stalagmites by an interval of strongly negative isotope ratios and increased growth rate. This contrasts with less negative δ18O and δ13C, and slow growth, interpreted as dry and cold climate, during much of MIS 2. This difference between MIS 2 and MIS 4 provides an explanation for why glacial moraines in the Southern Alps of MIS 4 age lie beyond those deposited during the last glacial maximum (MIS 2). Heinrich events, with the exception of H0 (the Younger Dryas), are interpreted from high-resolution South Island stalagmite HW05-3, from Hollywood Cave, West Coast, as times of wetter and cooler climate. Minima in δ18O and δ13C (wet periods) occurred at 67.7-61.0, 56-55, 50.5-47.5, 40-39, 30.5-29, 25.5-24.3 and 16.1-15. kyr B.P. matching Heinrich events H6-H1 (including H5a) respectively. This demonstrates a robust teleconnection between events in the North Atlantic and New Zealand climate. Minima in δ18O also occurred at similar times in less well-dated North Island stalagmite RK05-3 from Ruakuri Cave, Waitomo. Speleothems from low-latitudes have revealed that Heinrich events forced southerly displacement of the Intertropical Convergence Zone. This caused steepening of the temperature gradient across mid-southern latitudes, increased westerly circulation and resulted in wet conditions on the west coast of both islands. Immediately following H1 in the HW05-3 stable isotope profiles is another excursion to more negative isotopic values, suggesting wet and cold climate, lasting from 14.6 to 13.0 kyr B.P. Such a climate on the West Coast at this time has been previously suggested from glacier advance (e.g. Waiho Loop moraine) and decreased abundance of tall trees on the landscape. This event occurred too early to be a response to H0, but is synchronous with a return to cool climate in Antarctica. Thus West Coast climate appears to have been sensitive to changes in Antarctica as well as the North Atlantic. Isotopic minima (wet and cool climate) in South Island stalagmite GT05-5, which formed during the Holocene, first occurred 4.6 kyr B.P. This began a series of four oscillations in isotope ratios, the last terminating when the stalagmite was collected (2006). Onset of these oscillations is associated with initiation of ice advance in the Southern Alps, and beginning of the Neoglacial. The last oscillation displays enriched isotope ratios lasting from 1.2 to 0.8 kyr B.P. succeeded by depleted ratios lasting until 0.15 kyr B.P., mirroring the Medieval Climate Optimum and Little Ice Age, respectively, of European palaeoclimate records.