Stable oxygen, hydrogene and chlorine isotopes of mid-Atlantic abyssal peridotites

Serpentinized abyssal peridotites sampled by the Ocean Drilling Program Leg 209 along the mid-Atlantic Ridge near the 15°20'N Fracture Zone have been analyzed for oxygen, hydrogen, and chlorine isotope compositions in order to determine isotopic behavior under a wide range of serpentinization conditions and place constraints on fluid history. Oxygen and hydrogen thermometry suggests peak serpentinization temperatures of 300-500°C. Serpentine separates have low deltaD values possibly due to a magmatic fluid component or low-temperature exchange during seafloor weathering. Chlorine geochemistry focused on three holes: 1274A and 1272A (serpentinized peridotites) and 1268A (serpentinite locally altered to talc). Concentrations of both, water-soluble chloride (WSC) and structurally bound chloride (SBC) are significantly lower at Hole 1268A compared to Holes 1274A and 1272A. The delta37Cl values for WSC and SBC of serpentinites in Holes 1274A and 1272A are slightly positive (avg. WSC = 0.20 per mil, n = 22 and avg. SBC = 0.35 per mil, n = 22), representing typical seawater-hydration conditions commonly determined for abyssal peridotite. The SBC of serpentinites from Hole 1268A are also positive (avg. = 0.63 per mil); whereas, the SBC in talc-dominated samples is negative (avg. = -1.22 per mil). The WSC of both talc- and serpentine-dominated samples are also negative (avg. = -0.15 per mil). We interpret the chlorine isotope data to preserve a record of multiple fluid events. As seawater hydrated the peridotite, 37Cl was preferentially incorporated into the forming serpentine and water-soluble salts, yielding similar delta37Cl values on a regional scale as sampled by Holes 1268A, 1274A and 1272A. The resultant pore fluid was left depleted in 37Cl. Locally (Hole 1268A), this evolved fluid was remobilized possibly due to the initiation of hydrothermal circulation in response to emplacement of a mafic magma body. The low delta37Cl pore fluids attained elevated SiO2 and sulfur concentrations due to interaction with the gabbroic intrusion and, when ascending through the surrounding serpentinite, caused formation of isotopically negative talc. This secondary fluid also flushed the preserved serpentinite of its previously formed salts, resulting in negative delta37Cl WSC values. The delta37Cl SBC values of the serpentinite samples remained unmodified by reaction with the secondary fluid.

Radiogenic neodymium, strontium and lead isotopes of authigenic and detrital sedimentary phases and stable oxygen and carbon isotopes of benthic foraminifera from gravity cores SO213-59-2 and SO213-60-1 (central South Pacific).

The South Pacific is a sensitive location for the variability of the global oceanic thermohaline circulation given that deep waters from the Atlantic Ocean, the Southern Ocean, and the Pacific Basin are exchanged. Here we reconstruct the deep water circulation of the central South Pacific for the last two glacial cycles (from 240,000 years ago to the Holocene) based on radiogenic neodymium (Nd) and lead (Pb) isotope records complemented by benthic stable carbon data obtained from two sediment cores located on the flanks of the East Pacific Rise. The records show small but consistent glacial/interglacial changes in all three isotopic systems with interglacial average values of -5.8 and 18.757 for epsilon Nd and 206Pb/204Pb, respectively, whereas glacial averages are -5.3 and 18.744. Comparison of this variability of Circumpolar Deep Water (CDW) to previously published records along the pathway of the global thermohaline circulation is consistent with reduced admixture of North Atlantic Deep Water to CDW during cold stages. The absolute values and amplitudes of the benthic delta13C variations are essentially indistinguishable from other records of the Southern Hemisphere and confirm that the low central South Pacific sedimentation rates did not result in a significant reduction of the amplitude of any of the measured proxies. In addition, the combined detrital Nd and strontium (87Sr/86Sr) isotope signatures imply that Australian and New Zealand dust has remained the principal contributor of lithogenic material to the central South Pacific.

(Table 1) Oxygen and carbon isotopes for planktonic foraminifers at DSDP Hole 64-480

During the cleaning of the HPC core surfaces from Hole 480 for photography, the material removed was conserved carefully in approximately 10 cm intervals (by K. Kelts); this material was made available to us in the hope that it would be possible to obtain oxygen isotope stratigraphy for the site. The samples were, of course, somewhat variable in size, but the majority were probably between 5 and 10 cm**3. Had this been a normal marine environment, such sample sizes would have contained abundant planktonic foraminifers together with a small number of benthics. However, this is clearly not the case, for many samples contained no foraminifers, whereas others contained more benthics than planktonics. Among the planktonic foraminifers the commonest species are Globigerina bulloides, Neogloboquadrina dutertrei, and N. pachyderma. A few samples contain a more normal fauna with Globigerinoides spp. and occasional Globorotalia spp. Sample 480-3-3, 20-30 cm contained Globigerina rubescens, isolated specimens of which were noted in a few other samples in Cores 3,4, and 5. This is a particularly solution-sensitive species; in the open Pacific it is only found widely distributed at horizons of exceptionally low carbonate dissolution, such as. the last glacial-to-interglacial transition.

Stable oxygen and carbon isotopes ratios of sediment core GeoB9528-3

The carbon isotopic composition of individual plant leaf waxes (a proxy for C3 vs. C4 vegetation) in a marine sediment core collected from beneath the plume of Sahara-derived dust in northwest Africa reveals three periods during the past 192,000 years when the central Sahara/Sahel contained C3 plants (likely trees), indicating substantially wetter conditions than at present. Our data suggest that variability in the strength of Atlantic meridional overturning circulation (AMOC) is a main control on vegetation distribution in central North Africa, and we note expansions of C3 vegetation during the African Humid Period (early Holocene) and within Marine Isotope Stage (MIS) 3 (approx. 50-45 ka) and MIS 5 (approx. 120-110 ka). The wet periods within MIS 3 and 5 coincide with major human migration events out of sub-Saharan Africa. Our results thus suggest that changes in AMOC influenced North African climate and, at times, contributed to amenable conditions in the central Sahara/Sahel, allowing humans to cross this otherwise inhospitable region.

(Table 1) Oxygen and carbon isotopes for foraminiferal taxa at DSDP Hole 76-540

We analyzed the oxygen and carbon isotopic composition of planktonic and benthic foraminifers picked from 13 late Eocene to late Oligocene samples from DSDP Site 540 (23°49.73'N, 84°22.25'W, 2926 m water depth) from the Gulf of Mexico. An enrichment occurs in 18O of about 0.5 to 0.8 per mil in both benthic foraminifers and surface-dwelling planktonic foraminifers between the latest Eocene and early Oligocene. This early Oligocene maximum is followed by lower 18O values. A 1.2 per mil d13C decrease in both benthic and planktonic foraminiferal data occurs from the late Eocene to the late Oligocene. There is a correspondence of the 13C signal to deep-sea records; however, the amplitude of this change is greater than previously seen in deep-sea cores, possibly as a result of proximity to terrestrial sources of carbon. The covarying isotopic changes in both benthic and planktonic foraminifers suggest global causes, such as ice volume increases and increased terrestrial carbon input to the ocean. However, during the latter part of the record (early-late Oligocene), the increases in the benthic 18O without accompanying increases observed with planktonic foraminifers suggest that changes in only one part of the system occurred; one potential explanation being a decrease in bottom-water temperatures without concomitant changes in the surface waters. The 18O differences between species of planktonic foraminifers and the difference between planktonic and benthic 18O data indicate that diagenesis problems are minimal. These preliminary results are encouraging given that these cores are partially lithified.

Diatom oxygen and silicon isotopes data from IODP Hole 323-U1341B in the Bering Sea through the late Pliocene and over the onset of major Northern Hemisphere Glaciation

The Bering Sea is one of the most biologically productive regions in the marine system and plays a key role in regulating the flow of waters to the Arctic Ocean and into the subarctic North Pacific Ocean. Cores from Integrated Ocean Drilling Program (IODP) Expedition 323 to the Bering Sea provide the first opportunity to obtain reconstructions from the region that extend back to the Pliocene. Previous research at Bowers Ridge, south Bering Sea, has revealed stable levels of siliceous productivity over the onset of major Northern Hemisphere Glaciation (NHG) (circa 2.85-2.73 Ma). However, diatom silica isotope records of oxygen (d18Odiatom) and silicon (d30Sidiatom) presented here demonstrate that this interval was associated with a progressive increase in the supply of silicic acid to the region, superimposed on shift to a more dynamic environment characterized by colder temperatures and increased sea ice. This concluded at 2.58 Ma with a sharp increase in diatom productivity, further increases in photic zone nutrient availability and a permanent shift to colder sea surface conditions. These transitions are suggested to reflect a gradually more intense nutrient leakage from the subarctic northwest Pacific Ocean, with increases in productivity further aided by increased sea ice- and wind-driven mixing in the Bering Sea. In suggesting a linkage in biogeochemical cycling between the south Bering Sea and subarctic Northwest Pacific Ocean, mainly via the Kamchatka Strait, this work highlights the need to consider the interconnectivity of these two systems when future reconstructions are carried out in the region.

Measurement of total body water (TBW) and total energy expenditure (TEE) using stable isotopes

Understanding the relationship between diet, physical activity and health in humans requires accurate measurement of body composition and daily energy expenditure. Stable isotopes provide a means of measuring total body water and daily energy expenditure under free-living conditions. While the use of isotope ratio mass spectrometry (IRMS) for the analysis of 2H (Deuterium) and 18O (Oxygen-18) is well established in the field of human energy metabolism research, numerous questions remain regarding the factors which influence analytical and measurement error using this methodology. This thesis was comprised of four studies with the following emphases. The aim of Study 1 was to determine the analytical and measurement error of the IRMS with regard to sample handling under certain conditions. Study 2 involved the comparison of TEE (Total daily energy expenditure) using two commonly employed equations. Further, saliva and urine samples, collected at different times, were used to determine if clinically significant differences would occur. Study 3 was undertaken to determine the appropriate collection times for TBW estimates and derived body composition values. Finally, Study 4, a single case study to investigate if TEE measures are affected when the human condition changes due to altered exercise and water intake. The aim of Study 1 was to validate laboratory approaches to measure isotopic enrichment to ensure accurate (to international standards), precise (reproducibility of three replicate samples) and linear (isotope ratio was constant over the expected concentration range) results. This established the machine variability for the IRMS equipment in use at Queensland University for both TBW and TEE. Using either 0.4mL or 0.5mL sample volumes for both oxygen-18 and deuterium were statistically acceptable (p>0.05) and showed a within analytical variance of 5.8 Delta VSOW units for deuterium, 0.41 Delta VSOW units for oxygen-18. This variance was used as “within analytical noise” to determine sample deviations. It was also found that there was no influence of equilibration time on oxygen-18 or deuterium values when comparing the minimum (oxygen-18: 24hr; deuterium: 3 days) and maximum (oxygen-18: and deuterium: 14 days) equilibration times. With regard to preparation using the vacuum line, any order of preparation is suitable as the TEE values fall within 8% of each other regardless of preparation order. An 8% variation is acceptable for the TEE values due to biological and technical errors (Schoeller, 1988). However, for the automated line, deuterium must be assessed first followed by oxygen-18 as the automated machine line does not evacuate tubes but merely refills them with an injection of gas for a predetermined time. Any fractionation (which may occur for both isotopes), would cause a slight elevation in the values and hence a lower TEE. The purpose of the second and third study was to investigate the use of IRMS to measure the TEE and TBW of and to validate the current IRMS practices in use with regard to sample collection times of urine and saliva, the use of two TEE equations from different research centers and the body composition values derived from these TEE and TBW values. Following the collection of a fasting baseline urine and saliva sample, 10 people (8 women, 2 men) were dosed with a doubly labeled water does comprised of 1.25g 10% oxygen-18 and 0.1 g 100% deuterium/kg body weight. The samples were collected hourly for 12 hrs on the first day and then morning, midday, and evening samples were collected for the next 14 days. The samples were analyzed using an isotope ratio mass spectrometer. For the TBW, time to equilibration was determined using three commonly employed data analysis approaches. Isotopic equilibration was reached in 90% of the sample by hour 6, and in 100% of the sample by hour 7. With regard to the TBW estimations, the optimal time for urine collection was found to be between hours 4 and 10 as to where there was no significant difference between values. In contrast, statistically significant differences in TBW estimations were found between hours 1-3 and from 11-12 when compared with hours 4-10. Most of the individuals in this study were in equilibrium after 7 hours. The TEE equations of Prof Dale Scholler (Chicago, USA, IAEA) and Prof K.Westerterp were compared with that of Prof. Andrew Coward (Dunn Nutrition Centre). When comparing values derived from samples collected in the morning and evening there was no effect of time or equation on resulting TEE values. The fourth study was a pilot study (n=1) to test the variability in TEE as a result of manipulations in fluid consumption and level of physical activity; the magnitude of change which may be expected in a sedentary adult. Physical activity levels were manipulated by increasing the number of steps per day to mimic the increases that may result when a sedentary individual commences an activity program. The study was comprised of three sub-studies completed on the same individual over a period of 8 months. There were no significant changes in TBW across all studies, even though the elimination rates changed with the supplemented water intake and additional physical activity. The extra activity may not have sufficiently strenuous enough and the water intake high enough to cause a significant change in the TBW and hence the CO2 production and TEE values. The TEE values measured show good agreement based on the estimated values calculated on an RMR of 1455 kcal/day, a DIT of 10% of TEE and activity based on measured steps. The covariance values tracked when plotting the residuals were found to be representative of “well-behaved” data and are indicative of the analytical accuracy. The ratio and product plots were found to reflect the water turnover and CO2 production and thus could, with further investigation, be employed to identify the changes in physical activity.

Isotopic proxies for microbial and environmental change : insights hydrogen isotopes and the Ediacaran Khufai Formation

Microbes have profoundly influenced the Earth’s environments through time. Records of these interactions come primarily from the development and implementation of proxies that relate known modern processes to chemical signatures in the sedimentary record. This thesis is presented in two parts, focusing first on novel proxy development in the modern and second on interpretation of past environments using well-established methods. Part 1, presented in two chapters, builds on previous observations that different microbial metabolisms produce vastly different lipid hydrogen isotopic compositions. Chapter 1 evaluates the potential environmental expression of metabolism-based fractionation differences by exploiting the natural microbial community gradients in hydrothermal springs. We find a very large range in isotopic composition that can be demonstrably linked to the microbial source(s) of the fatty acids at each sample site. In Chapter 2, anaerobic culturing techniques are used to evaluate the hydrogen isotopic fractionations produced by anaerobic microbial metabolisms. Although the observed fractionation patterns are similar to those reported for aerobic cultures for some organisms, others show large differences. Part 2 changes focus from the modern to the ancient and uses classical stratigraphic methods combined with isotope stratigraphy to interpret microbial and environmental changes during the latest Precambrian Era. Chapter 3 presents a detailed characterization of the facies, parasequence development, and stratigraphic architecture of the Ediacaran Khufai Formation. Chapter 4 presents measurements of carbon, oxygen, and sulfur isotopic ratios in stratigraphic context. Large oscillations in the isotopic composition of sulfate constrain the size of the marine sulfate reservoir and suggest incorporation of an enriched isotopic source. Because this data was measured in stratigraphic context, we can assert with confidence that these isotopic shifts are not related to stratigraphic surfaces or facies type but instead reflect the evolution of the ocean through time. This data integrates into the chemostratigraphic global record and contributes to the emerging picture of changing marine chemistry during the latest Precambrian Era.

Gas-phase isothermal chromatography with short-lived technetium isotopes

In order to study the gas-phase chemical behavior of transactinides, an on-line isothermal chromatography apparatus has been developed and applied to separate short-lived technetium isotopes in the form of TcO3 from fission products. The fission products from a Cf-252 source were continuously and rapidly transported through the capillary to the isothermal chromatography apparatus using the N-2/KBr gas-jet techniques. Volatile oxide molecules were formed at the reaction zone kept at 900 degrees C since a trace amount of oxygen existed in the N-2 carrier gas. With the new developed isothermal chromatography apparatus, a selective separation of Tc from fission products was achieved. After isothermal chromatographic separation, Tc-101,Tc-103,Tc-104,Tc-105,Tc-106,Tc-107,Tc-108 were dominantly observed together with their Ru daughters in the gamma-spectrum, The chemical yields of Tc-101, and Tc-104 and Tc-105 isotopes with longer half-lives are about 55-57%, and those of Tc-103, Tc-106 and Tc-108 isotopes with shorter half-lives dropped down to 25-28%. The adsorption enthalpy of the investigated compounds on quartz surfaces was determined to be -150 +/- 5 kJ/mol by fitting the measured retention curves with a Monte Carlo model. The observed species of technetium oxide is attributed to TcO3, which is in good agreement with previous experimental results. That means our system worked properly and it can be used to investigate the gas-phase chemical behavior of transactinides.

Caractérisation du cycle et des sources d'azote dans les lacs tempérés par l'utilisation d'isotopes stables

Nous avons étudié l’application de plusieurs mesures d’isotopes stables afin de caractériser les processus du cycle de l’azote et les sources d’azote dans les lacs tempérés à diverses échelles spatiales et temporelles. Les résultats d’une étude à travers 65 lacs sur un gradient trophique ont démontré que le ratio d’isotopes stables d’azote (δ15N) des sédiments de surface est un indicateur de l’importance relative des sources d’azote anthropique, mais que ce ratio peut être altéré par la diagenèse. La mesure du δ15N des sédiments demeure néanmoins un outil permettant de déterminer à long terme le changement des charges en azote anthropique aux écosystèmes lacustres et les causes de l’eutrophisation de ces systèmes. Nos résultats d’une étude sur la variation saisonnière de plusieurs isotopes stables dans trois lacs peu profonds situés sur un gradient trophique et ayant différents régimes de stratification ont démontré que cette approche est prometteuse dans les lacs mésotrophes et stratifiés. Dans ces systèmes, le δ15N de la matière organique particulaire (MOP) aurait le potentiel de déterminer les sources d’azote assimilées par le phytoplancton. Cependant les mesures d’isotopes stables du carbone (δ13C) et du ratio C:N indiquent que les apports de matières organiques du bassin versant peuvent altérer les relations observées. Nous avons également constaté une déviation de la relation 1:1 entre les isotopes stables d’azote et d’oxygène (δ18O) du nitrate (NO3-) indiquant son assimilation et sa nitrification simultanée. Cette application est particulièrement prometteuse puisque la nitrification est méconnue dans les lacs et peut exacerber les effets de l’eutrophisation.

Essai de détection de processus migratoires à travers les isotopes de strontium et d’oxygène : étude des restes humains du cimetière Saint-Matthew (Québec, 1771-1860)

Afin de distinguer les immigrants de première génération des individus nés à Québec et de discuter de l’identité des immigrants de cette ville aux XVIIIe et XIXe siècles, trente-quatre squelettes humains exhumés du cimetière protestant Saint-Matthew (Québec, 1771-1860) ont fait l’objet d’analyses ostéologiques et isotopiques du strontium (87Sr/86Sr) et de l’oxygène (δ18O). Les teneurs obtenues, bien que moins précises que les données historiques, ont permis de distinguer trois groupes d’origine, soit les individus nés à Québec (N = 12), les immigrants de première génération provenant le plus probablement des îles Britanniques et du nord de la France (N = 19) et les immigrants de première génération dont l’origine ne peut être précisée (N = 3). De plus, l’origine écossaise de certains individus a pu être suggérée en fonction de compositions isotopiques variant entre -10,0 et -9,09 % vs VSMOW. La comparaison des groupes d’origine à des données provenant de sources historiques et d’une étude antérieure a permis de dresser un portrait de l’identité des immigrants, à la fois sur les plans populationnel et individuel. De plus, les compositions isotopiques (δ18O, 87Sr/86Sr, δ13C et δ15N) nous laissent croire qu’au moins un individu pourrait être d’origine amérindienne et qu’un autre proviendrait d’une partie de l’Europe plus appauvrie en 18O (possiblement un pays scandinave ou une région alpine). La distribution spatiale des sépultures nous a également permis d’émettre des hypothèses sur les liens familiaux et sociaux d’immigrants inhumés en caveaux ou entassés de façon particulièrement modeste.