(Table 2) Stable oxgen and carbon isotopic record of planktonic foraminifera from DSDP Hole 30-289

Oxygen and carbon isotopic data for 13 planktonic foraminifers from the Miocene of DSDP Site 289 strongly support the idea that the species have a preferred depth habitat and that their depth relationships remained largely unchanged during the Miocene. However, the relative depth rankings of Globorotalia (Menardella) menardii and Globorotalia (Menardella) limbata changed from deep to intermediate and from deep to shallow, respectively, during the late Miocene between ~9.9 and 7.5 Ma.

Use of 3D visualisation to enhance groundwater stable isotope data and its interpretation, Lockyer Valley, southeast Queensland

The use of stable isotope ratios δ18O and δ2H are well established in assessment of groundwater systems and their hydrology. The conventional approach is based on x/y plots and relation to various MWL’s, and plots of either ratio against parameters such as Clor EC. An extension of interpretation is the use of 2D maps and contour plots, and 2D hydrogeological vertical sections. An enhancement of presentation and interpretation is the production of “isoscapes”, usually as 2.5D surface projections. We have applied groundwater isotopic data to a 3D visualisation, using the alluvial aquifer system of the Lockyer Valley. The 3D framework is produced in GVS (Groundwater Visualisation System). This format enables enhanced presentation by displaying the spatial relationships and allowing interpolation between “data points” i.e. borehole screened zones where groundwater enters. The relative variations in the δ18O and δ2H values are similar in these ambient temperature systems. However, δ2H better reflects hydrological processes, whereas δ18O also reflects aquifer/groundwater exchange reactions. The 3D model has the advantage that it displays borehole relations to spatial features, enabling isotopic ratios and their values to be associated with, for example, bedrock groundwater mixing, interaction between aquifers, relation to stream recharge, and to near-surface and return irrigation water evaporation. Some specific features are also shown, such as zones of leakage of deeper groundwater (in this case with a GAB signature). Variations in source of recharging water at a catchment scale can be displayed. Interpolation between bores is not always possible depending on numbers and spacing, and by elongate configuration of the alluvium. In these cases, the visualisation uses discs around the screens that can be manually expanded to test extent or intersections. Separate displays are used for each of δ18O and δ2H and colour coding for isotope values.

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.

Determination of coastal ground and surface water processes and character by use of hydrochemistry and stable isotopes, Fraser Coast, Queensland

This study was part of an integrated project developed in response to concerns regarding current and future land practices affecting water quality within coastal catchments and adjacent marine environments. Two forested coastal catchments on the Fraser Coast, Australia, were chosen as examples of low-modification areas with similar geomorphological and land-use characteristics to many other coastal zones in southeast Queensland. For this component of the overall project, organic , physico-chemical (Eh, pH and DO), ionic (Fe2+, Fe3+), and isotopic (ä13CDIC, ä15NDIN ä34SSO4) data were used to characterise waters and identify sources and processes contributing to concentrations and form of dissolved Fe, C, N and S within the ground and surface waters of these coastal catchments. Three sites with elevated Fe concentrations are discussed in detail. These included a shallow pool with intermittent interaction with the surface water drainage system, a monitoring well within a semi-confined alluvial aquifer, and a monitoring well within the fresh/saline water mixing zone adjacent to an estuary. Conceptual models of processes occurring in these environments are presented. The primary factors influencing Fe transport were; microbial reduction of Fe3+ oxyhydroxides in groundwaters and in the hyporheic zone of surface drainage systems, organic input available for microbial reduction and Fe3+ complexation, bacterial activity for reduction and oxidation, iron curtain effects where saline/fresh water mixing occurs, and variation in redox conditions with depth in ground and surface water columns. Data indicated that groundwater seepage appears a more likely source of Fe to coastal waters (during periods of low rainfall) via tidal flux. The drainage system is ephemeral and contributes little discharge to marine waters. However, data collected during a high rainfall event indicated considerable Fe loads can be transported to the estuary mouth from the catchment.

Development of a stable isotope index to assess decadal-scale vegetation change and application to woodlands of the Burdekin catchment, Australia

Forty-four study sites were established in remnant woodland in the Burdekin River catchment in tropical north-east Queensland, Australia, to assess recent (decadal) vegetation change. The aim of this study was further to evaluate whether wide-scale vegetation 'thickening' (proliferation of woody plants in formerly more open woodlands) had occurred during the last century, coinciding with significant changes in land management. Soil samples from several depth intervals were size separated into different soil organic carbon (SOC) fractions, which differed from one another by chemical composition and turnover times. Tropical (C4) grasses dominate in the Burdekin catchment, and thus δ13C analyses of SOC fractions with different turnover times can be used to assess whether the relative proportion of trees (C3) and grasses (C4) had changed over time. However, a method was required to permit standardized assessment of the δ13C data for the individual sites within the 13 Mha catchment, which varied in soil and vegetation characteristics. Thus, an index was developed using data from three detailed study sites and global literature to standardize individual isotopic data from different soil depths and SOC fractions to reflect only the changed proportion of trees (C3) to grasses (C3) over decadal timescales. When applied to the 44 individual sites distributed throughout the Burdekin catchment, 64% of the sites were shown to have experienced decadal vegetation thickening, while 29% had remained stable and the remaining 7% had thinned. Thus, the development of this index enabled regional scale assessment and comparison of decadal vegetation patterns without having to rely on prior knowledge of vegetation changes or aerial photography.

Environmental and climatic dependences of stable isotope ratios in tree rings on different temporal scales

This work examines stable isotope ratios of carbon, oxygen and hydrogen in annual growth rings of trees. Isotopic composition in wood cellulose is used as a tool to study past climate. The method benefits from the accurate and precise dating provided by dendrochronology. In this study the origin, nature and the strength of climatic correlations are studied on different temporal scales and at different sites in Finland. The origin of carbon isotopic signal is in photosynthetic fractionation. The basic physical and chemical fractionations involved are reasonably well understood. This was confirmed by measuring instantaneous photosynthetic discrimination on Scots pine (Pinus sylvestris L.). The internal conductance of CO2 was recognized to have a significant impact on the observed fractionation, and further investigations are suggested to quantify its role in controlling the isotopic signal of photosynthates. Isotopic composition of the produced biomass can potentially be affected by variety of external factors that induce physiological changes in trees. Response of carbon isotopic signal in tree ring cellulose to changes in resource availability was assessed in a manipulation experiment. It showed that the signal was relatively stable despite of changes in water and nitrogen availability to the tree. Palaeoclimatic reconstructions are typically based on functions describing empirical relationship between isotopic and climatic parameters. These empirical relationships may change depending on the site conditions, species and timeframe studied. Annual variation in Scots pine tree ring carbon and oxygen isotopic composition was studied in northern and in central eastern Finland and annual variation in tree ring latewood carbon, oxygen and hydrogen isotopic ratio in Oak (Quercus robur L.) was studied in southern Finland. In all of the studied sites at least one of the studied isotope ratios was shown to record climate strongly enough to be used in climatic reconstructions. Using the observed relationships, four-century-long climate reconstructions from living Scots pine were created for northern and central eastern Finland. Also temporal stability of the relationships between three proxy indicators, tree ring growth and carbon and oxygen isotopic composition was studied during the four-hundred-year period. Isotope ratios measured from tree rings in Finland were shown to be sensitive indicators of climate. Increasing understanding of environmental controls and physiological mechanisms affecting tree ring isotopic composition will make possible more accurate interpretation of isotope data. This study also demonstrated that by measuring multiple isotopes and physical proxies from the same tree rings, additional information on tree physiology can be obtained. Thus isotopic ratios measured from tree ring cellulose provide means to improve the reliability of climate reconstructions.

Stable carbon isotope ratios in Asian elephant collagen: implications for dietary studies

Stable carbon isotope ratios in bone collagen have been used in a variety of dietary studies in modern and fossil animals, including humans. Inherent in the stable isotope technique is the assumption that the isotopic signature is a reflection of the diet and is persistent in collagen because this is a relatively inert protein. Carbon isotope analyses of bones from a southern Indian population of Asian elephant (Elephas maximus), a long-lived mammal that alternates seasonally between a predominantly C3 (browse) and C4 (grass) plant diet, showed two patterns that have important implications for dietary interpretation based on isotopic studies. Relative to the quantity of the two plant types consumed on average, the ?13C signal in collagen indicated that more carbon was incorporated from C3 plants, possibly due to their higher protein contribution. There was a much greater variance in ?13C values of collagen in sub-adult (range -10.5� to-22.7�, variance=14.51) compared to adult animals (range -16.0� to -20.3�, variance=1.85) pointing to high collagen turnover rates and non-persistent isotopic signatures in younger, growing animals. It thus seems important to correct for any significant relative differences in nutritive value of food types and also consider the age of an animal before drawing definite conclusions about its diet from isotope ratios.

Tracing the source of bottled water using stable isotope techniques

The Indian Summer Monsoon (ISM) precipitation recharges ground water aquifers in a large portion of the Indian subcontinent. Monsoonal precipitation over the Indian region brings moisture from the Arabian Sea and the Bay of Bengal (BoB). A large difference in the salinity of these two reservoirs, owing to the large amount of freshwater discharge from the continental rivers in the case of the BoB and dominating evaporation processes over the Arabian Sea region, allows us to distinguish the isotopic signatures in water originating in these two water bodies. Most bottled water manufacturers exploit the natural resources of groundwater, replenished by the monsoonal precipitation, for bottling purposes. The work presented here relates the isotopic ratios of bottled water to latitude, moisture source and seasonality in precipitation isotope ratios. We investigated the impact of the above factors on the isotopic composition of bottled water. The result shows a strong relationship between isotope ratios in precipitation (obtained from the GNIP data base)/bottled water with latitude. The approach can be used to predict the latitude at which the bottled water was manufactured. The paper provides two alternative approaches to address the site prediction. The limitations of this approach in identifying source locations and the uncertainty in latitude estimations are discussed. Furthermore, the method provided here can also be used as an important forensic tool for exploring the source location of bottled water from other regions. Copyright (C) 2011 John Wiley & Sons, Ltd.

Do stable isotopes in carbonate cement of Mio-Pleistocene Himalayan sediments record paleoecological and paleoclimatic changes?

Non-pedogenic carbonates, such as carbonate cement and nodules in the sandstones, are quite common in the terrestrial geological record. Unlike pedogenic carbonates, their stable isotope ratios lack investigations for paleo-climatic reconstructions. The present investigation therefore, explores the possibility of use of stable isotope studies of non-pedogenic carbonates from the Mb-Pleistocene Siwalik Group of sediments exposed in the Ramnagar sub-basin of the NW Himalaya. Petrographic studies reveal the dominance of micrite fabric in carbonate nodules both of pedogenic and non-pedogenic samples irrespective of specific stratigraphic unit However, calcite as cement in the sandstones shows the dominance of micrite fabric in the younger in age sediments. Seventy-two non-pedogenic carbonate samples from the carbonate nodules and cement in the Siwalik sandstones, ranging in age between similar to 1 Ma and 12.2 Ma, were analyzed for delta C-13 and delta O-18 values. The delta C-13 values vary from -24.77 parts per thousand to -1.1 parts per thousand and delta O-18 values vary from -15.34 parts per thousand to -7.81 parts per thousand. Pedogenic and non-pedogenic carbonates ranging in age between similar to 1 Ma and 6 Ma have largely similar delta C-13 values and the range of delta C-13 values indicate the dominance of C-4 type of vegetation. However, unlike pedogenic carbonates which showed the dominance of C-3 type of vegetation pre- 7 Ma on the basis of delta C-13 -depleted isotopic values (Singh et al., 2011), delta C-13 values are largely enriched in the corresponding aged non-pedogenic carbonates revealing no information on specific type of vegetation. Likewise, paleoprecipitational reconstructions from delta O-18 values in pedogenic carbonates showed a progressive increase in aridity from similar to 12 Ma to recent excluding short term increases in rainfall/monsoon intensity at around 10 Ma, 5 Ma, and 1.8 Ma (Singh et al., 2012). On the contrary, such reconstructions are not possible from the delta O-18 values of non-pedogenic carbonates and indeed the delta O-18 values of non-pedogenic carbonates are largely depleted to as much as 6 parts per thousand from the corresponding pedogenic carbonates. Such differences in delta C-13 and delta O-18 values of non-pedogenic carbonates from pedogenic carbonates are primarily due to the dependence of the former on groundwater conditions responsible for precipitating carbonate. Further, a comparison of isotopic values between non-pedogenic and pedogenic carbonates can be interpreted that post-6 Ma and pre-6 Ma non-pedogenic carbonates were largely formed by shallow and deep groundwater conditions respectively. The result of these investigative studies therefore, suggests that the stable delta C-13 and delta O-18 values of non-pedogenic carbonates, unlike the pedogenic carbonates and irrespective of nature of calcite fabric, showed their little importance in paleoclimatic and paleoecological reconstructions. (C) 2014 Elsevier B.V. All rights reserved.

Hydrographical characteristics and oxygen isotopic signatures of water in a coastal environment (Mangalore) along the southeastern Arabian Sea

Coastal marine environments are important links between the continents and the open ocean. The coast off Mangalore forms part of the upwelling zone along the southeastern Arabian Sea. The temperature, salinity, density, dissolved oxygen and stable oxygen isotope ratio (delta O-18) of surface waters as well as those of bottom waters off coastal Mangalore were studied every month from October 2010 to May 2011. The coastal waters were stratified in October and November due to precipitation and runoff. The region was characterised by upwelled bottom waters in October, whereas the region exhibited a temperature inversion in November. The surface and bottom waters presented almost uniform properties from December until April. The coastal waters were observed to be most dense in January and May. Comparatively cold and poorly oxygenated bottom waters during the May sampling indicated the onset of upwelling along the region. delta O-18 of the coastal waters successfully documented the observed variations in the hydrographical characteristics of the Mangalore coast during the monthly sampling period. We also noted that the monthly variability in the properties of the coastal waters of Mangalore was related to the hydrographical characteristics of the adjacent open ocean inferred from satellite-derived surface winds, sea surface height anomaly data and sea surface temperatures.

Sources of major ions and processes affecting the geochemical and isotopic signatures of subsurface waters along a tropical river, Southwestern India

Systematic monitoring of subsurface hydrogeochemistry has been carried out for a period of one year in a humid tropical region along the Nethravati-Gurupur River. The major ion and stable isotope (delta O-18 and delta H-2) compositions are used to understand the hydrogeochemistry of groundwater and its interaction with surface water. In the study, it is observed that intense weathering of source rocks is the major source of chemical elements to the surface and subsurface waters. In addition, agricultural activities and atmospheric contributions also control the major ion chemistry of water in the study area. There is a clear seasonality in the groundwater chemistry, which is related to the recharge and discharge of the hydrological system. On a temporal scale, there is a decrease in major cation concentrations during the monsoon which is a result of dilution of sources from the weathering of rock minerals, and an increase in anion concentrations which is contributed by the atmosphere, accompanied by an increase in water level during the monsoon. The stable isotope composition indicates that groundwater in the basin is of meteoric origin and recharged directly from the local precipitation during the monsoonal season. Soon after the monsoon, groundwater and surface water mix in the subsurface region. The groundwater feeds the surface water during the lean river flow season.

Stable isotope evidence for ca. 2.7-Ga-old Archean cap carbonates from the Dharwar Supergroup, southern India

Carbon isotope compositions of carbonate rocks from similar to 2.7-Ga-old Neoarchean Vanivilas Formation of the Dharwar Supergroup presented earlier by us are re-evaluated in this study, besides oxygen isotope compositions of a few silica dolomite pairs. The purpose of such a revisit assumes significance in view of recent field evidences that suggest a glaciomarine origin for the matrix-supported conglomerate member, the Talya conglomerate, which underlies the carbonate rocks of the Vanivilas Formation. An in-depth analysis of carbon isotope data reveals preservation of their pristine character despite the rocks having been subjected to metamorphism to different degrees (from lower greenschist to lower amphibolite facies). The dolomitic member of Vanivilas Formation of Marikanive area is characterized by highly depleted delta C-13 value (up to -5 parts per thousand VPDB) and merits as the Indian example of ca. 2.7-Ga-old cap carbonate. This inference is further supported by estimated low temperature of equilibration documented by a few silica dolomite pairs from the Vanivilas Formation collected near Kalche area. These pairs show evidence for oxygen isotopic equilibrium at low temperatures (similar to 0-20 degrees C) with depleted water (delta O-18 = -21 parts per thousand to -15 parts per thousand VSMOW) of glacial origin. We propose that the mineral pairs were deposited during the deglaciation period when the ocean temperature was in its gradual restoration phase. The dolomite of Marikanive area is the first record of cap carbonates from the Indian subcontinent with Neoarchean antiquity.

Isotopic and geochemical characterization of invader tilapia fishes from water bodies of West Bengal and Karnataka, India

The otoliths (N = 12) of freshwater invasive species tilapia (Tilapia mossambicus) collected from two water bodies located at Kolkata and Bangalore, India, were analyzed for stable isotopes (delta 18O, delta 14C) and major and trace elements in order to assess the suitability of using otoliths as a tracer of aquatic environmental changes. The stable isotope analysis was done using the dual inlet system of a Finnigan-MAT 253 isotope ratio mass spectrometer (Thermo-Fisher, Bremen, Germany). Concentrations of major and trace elements were determined using a Thermo X-Series II quadrupole mass spectrometer. The stable isotope composition in tilapia otolith samples from Bangalore and Kolkata water bodies are quite good agreeing with that of the respective lake/pond and rain water. Elemental composition revealed in a pattern of Ca > Fe > Na > Sr > K > Ba > Cr > Mg > As > Mn > Zn > Co > Cu > Cd > Pb. The otoliths from Kolkata pond water are more enriched in Ba, Zn, Pb, Mn, Se, Cu, Zn, Cd, and Ni whereas Cr and As were found to be higher in otolith samples from Bangalore lake. The enrichment factor (EF) values of Cr were higher for both the sampling location in comparison with other metals, although all the studied metals exhibited EF values >1. The PCA shows clustering of metals in the otolith which are related either with the metabolic and physiological attributes or waterborne source. The study demonstrated the potential of stable isotope techniques to distinguish otolith specimens from varied climatic zone, while elemental composition recorded the quality of water at both the locations. The role of climate driving the quality of water can be understood by detailed and continuous monitoring of otolith specimens in the future. Future method allows reconstruction of climate and water quality from old specimens from field exposures or museum collection.

Interlaboratory comparison of magnesium isotopic compositions of 12 felsic to ultramafic igneous rock standards analyzed by MC-ICPMS

To evaluate the interlaboratory mass bias for high-precision stable Mg isotopic analysis of natural materials, a suite of silicate standards ranging in composition from felsic to ultramafic were analyzed in five laboratories by using three types of multicollector inductively coupled plasma mass spectrometer (MC-ICPMS). Magnesium isotopic compositions from all labs are in agreement for most rocks within quoted uncertainties but are significantly (up to 0.3 parts per thousand in Mg-26/Mg-24, > 4 times of uncertainties) different for some mafic samples. The interlaboratory mass bias does not correlate with matrix element/Mg ratios, and the mechanism for producing it is uncertain but very likely arises from column chemistry. Our results suggest that standards with different matrices are needed to calibrate the efficiency of column chemistry and caution should be taken when dealing with samples with complicated matrices. Well-calibrated standards with matrix elements matching samples should be used to reduce the interlaboratory mass bias.