No / We examined multiple natural abundance isotope ratios of human hair to assess biological variability within and between geographic locations and, further, to determine how well these isotope values predict location of origin. Sampling locations feature differing seasonality and mobile populations as a robust test of the method. Serially-sampled hair from Cambridge, MA, USA, shows lower δ2 H and δ18 O variability over a one-year time course than model-predicted precipitation isotope ratios, but exhibits considerable differences between individuals. Along a ∼13° northsouth transect in the eastern USA (Brookline, MA, 42.3 ° N, College Park, MD, 39.0 ° N, and Gainesville, FL, 29.7 ° N) δ18 O in human hair shows relatively greater differences and tracks changes in drinking water isotope ratios more sensitively than δ2 H. Determining the domicile of humans using isotope ratios of hair can be confounded by differing variability in hair δ18 O and δ2 H between locations, differential incorporation of H and O into this protein and, in some cases, by tap water δ18 O and δ2 H that differ significantly from predicted precipitation values. With these caveats, randomly chosen people in Florida are separated from those in the two more northerly sites on the basis of the natural abundance isotopes of carbon, nitrogen, hydrogen, and oxygen. / This work was partially supported by the National Geospatial Agency under grant [HM1582-08-0024]. / Originally presented at the IAEA International Symposium on Isotope Hydrology: Revisiting Foundations and Exploring Frontiers, 11–15 May 2015, Vienna, Austria

Yes / Objectives: We compared δ15N and δ13C values from bone and dentine collagen profiles of individuals interred in famine‐related and attritional burials to evaluate whether individuals in medieval London who experienced nutritional stress exhibit enriched nitrogen in bone and tooth tissue. Dentine profiles were evaluated to identify patterns that may be indicative of famine during childhood and were compared with the age of enamel hypoplasia (EH) formation to assess whether isotopic patterns of undernutrition coincide with the timing of physiological stress. Materials and Methods: δ15N and δ13C isotope ratios of bone collagen were obtained from individuals (n = 128) interred in attritional and famine burials from a medieval London cemetery (c. 1120–1539). Temporal sequences of δ15N and δ13C isotope profiles for incrementally forming dentine collagen were obtained from a subset of these individuals (n = 21). Results: Results indicate that individuals from attritional graves exhibit significantly higher δ15N values but no significant differences were found between burial types for the sexes. Analyses of dentine profiles reveal that a lower proportion of famine burials exhibit stable dentine profiles and that several exhibit a pattern of opposing covariance between δ15N and δ13C. EH were also observed to have formed during or after the opposing covariance pattern for some individuals. Conclusions: The results of this study may reflect differences in diet between burial types rather than nutritional stress. Though nutritional stress could not be definitively identified using bone and dentine collagen, the results from dentine analysis support previous observations of biochemical patterns associated with nutritional stress during childhood. / Division of Behavioral and Cognitive Sciences. Grant Numbers: BCS‐1261682, BCS‐1540208. Office of the Vice President for Research, University of South Carolina. Grant Number: SPARC Fellowship Grant

Hydrogeochemical studies are generally qualitative in nature. The goal of this study is to investigate the possibility of quantitative interpretation of hydrogeochemistry by considering the chemical characteristics and the isotopic compositions of oxygen, hydrogen, and carbon of the water. This study examines ephemeral stream and well waters from Canada del Oro valley, southern Arizona. By chemical and isotopic considerations, this study finds that the change of chemical composition of the wash water was mainly due to water-rock interaction. The concentrations of dissolved constituents increase between 10 to 50% from upstream to downstream samples, while the evaporation loss of water is less than 3%. By chemical and isotopic considerations of the well waters, this study identifies three recharge waters in the CDO ground-water system. The chemical and water isotopic compositions of the well waters are results of mixing between these three recharge waters and subsequent dissolution of the aquifer. By thermodynamic consideration, albite, kaolinite, montmorillonite, and calcite are the main phases that influence the chemical characteristics of this ground-water system. Simulations with the computer program PHREEQE verifies the above conclusions. The mechanisms that influence the chemical and carbon isotopic compositions of the water are quite different in a system open to a CO2 gas reservoir than in a closed system. Deines, Langmuir, and Harmon (1974) derived a set of chemical-isotopic equations to calculate the carbon isotopic composition of water under open system condition. Wigley, Plummer, and Pearson (1978) formulated a mass transfer equation to calculate the change of carbon isotopic composition of natural water in closed system environment. This study implements these two type of equations as a subroutine--CSOTOP to the computer program PHREEQE. With this PHREEQE-CSOTOP package, the evolution of carbon chemical and isotopic composition of natural water can be conveniently modeled from open to closed system conditions. This study also uses this package to date water samples from the Tucson basin, and finds that choice of reaction path may cause a difference in carbon-14 age of up to a few thousand years. This study concludes that it is possible to rigorously interpret hydrogeochemistry in a quantitative way. With sufficient measurements to define the reaction path, followed by thermodynamic consideration, chemical-isotopic evaluation, and computer modeling, one should be able to achieve this goal.

The main goal of the work presented in this thesis is to improve the reliability of existing methods for speciation analysis of organotin compounds Species-specific isotope dilution (SSID) calibration in combination with gas chromatography – inductively coupled plasma mass spectrometry was used to investigate the transformation of phenyltin species during sample preparation. Isotope-enriched phenyltin species were synthesized from corresponding isotope-enriched tin metals. SSID with a mixture of phenyltin species (PhTs) from one isotope was used to evaluate different extraction procedures for the determination of PhTs in fresh water sediment. Preparative liquid chromatography was used to produce single isotope-enriched phenyltin species making a multi-isotope spike (MI) SSID calibration possible. Different extraction procedures for the analysis of phenyltin species in biological samples were evaluated by applying MI-SSID. Degradation of TPhT and DPhT during sample extraction was observed and quantified. Accurate results were therefore obtained. A sample preparation procedure using mild extraction conditions with reasonable recoveries is described. The stability of organotin standards was investigated under different storage conditions. Mono- and diphenyltin were found to be redistributed and degraded during storage in methanol but were stabilized in sodium acetate/ acetic acid. A fast redistribution between monobutyl- and diphenyl tin has been observed and therefore it is therefore recommended that standards be derivatized as soon as possible after butyl- and phenyltin standards are mixed. Included in the thesis is also an investigation of the analytical potential of using instrumentation based on atomic absorption spectrometry (AAS) for speciation analysis of organotin compounds. The method was based on gas chromatographic separation, atomization in a quartz tube and detection by line source (LS) AAS and for comparison, by state of the art continuum source (CS) AAS. Analytical performances of CSAAS system were found to be better compared to LSAAS.

Rice grows in saturated soil water condition and its requirement for water is highest amongst other cereal crops. In India, the southwest monsoon wind regime brings rainfall that provides a favourable environment for rice cultivation. Thus, there is significant dependency ofrice production on the southwest monsoon rainfall. Being a crop that grows across diverse climatic regions in India ranging from the humid to semi-arid, it offers possibility to explore therelationship between stable isotopic compositions in the grain organic matter with the climaticfactors relevant for its growth. In this thesis, we measured the isotopic compositions of oxygen, hydrogen and carbon of several rice genotypes that were cultivated during the southwest monsoon in diverse climatic regions across the Indian landmass. These isotopic values were then compared with the seasonalaverage values of climate factors such as relative humidity and temperature. Together with thiswe also studied the dependency of the oxygen isotope composition of the grain OM (δ18OOM) onthat of the source water (δ18OSW). Upon removal of δ18OSW effect from δ18OOM, we obtained astrong and significant relationship between the 18O enrichment in grain organic matter (definedas 18OOM) with relative humidity. The gradient recorded was 0.45‰ shift in 18OOM with 1%change in the relative humidity level. This relationship can potentially be used to estimate thepast variations in relative humidity (and by extension, can provide a measure of monsoon rainfallvariations). We further validated this relationship based on experiments carried out in aglasshouse where all the physical factors were well-monitored. Together with this, carbonisotopic composition measured in the rice grain organic matter were used to infer the water useefficiency of rice grown in different climatic settings. The stable isotope approach was furtherimplemented for studying the archaeological rice grains recovered from archaeological sites. Analysis of carbon isotopic composition of archaeological rice grains from seven archaeologicalsites (Balu, Kanmer, Ojiyana, Lahuradewa, JognaKhera, Hulas and Kunal), belonging to theHarappan civilization and other contemporary cultures provided a new suit of data on quantitativeestimate of the hydroclimatic condition (specifically relative humidity) and water availabilityduring the existence of this civilization.

Rice grows in saturated soil water condition and its requirement for water is highest amongst other cereal crops. In India, the southwest monsoon wind regime brings rainfall that provides a favourable environment for rice cultivation. Thus, there is significant dependency ofrice production on the southwest monsoon rainfall. Being a crop that grows across diverse climatic regions in India ranging from the humid to semi-arid, it offers possibility to explore therelationship between stable isotopic compositions in the grain organic matter with the climaticfactors relevant for its growth. In this thesis, we measured the isotopic compositions of oxygen, hydrogen and carbon of several rice genotypes that were cultivated during the southwest monsoon in diverse climatic regions across the Indian landmass. These isotopic values were then compared with the seasonalaverage values of climate factors such as relative humidity and temperature. Together with thiswe also studied the dependency of the oxygen isotope composition of the grain OM (δ18OOM) onthat of the source water (δ18OSW). Upon removal of δ18OSW effect from δ18OOM, we obtained astrong and significant relationship between the 18O enrichment in grain organic matter (definedas 18OOM) with relative humidity. The gradient recorded was 0.45‰ shift in 18OOM with 1%change in the relative humidity level. This relationship can potentially be used to estimate thepast variations in relative humidity (and by extension, can provide a measure of monsoon rainfallvariations). We further validated this relationship based on experiments carried out in aglasshouse where all the physical factors were well-monitored. Together with this, carbonisotopic composition measured in the rice grain organic matter were used to infer the water useefficiency of rice grown in different climatic settings. The stable isotope approach was furtherimplemented for studying the archaeological rice grains recovered from archaeological sites. Analysis of carbon isotopic composition of archaeological rice grains from seven archaeologicalsites (Balu, Kanmer, Ojiyana, Lahuradewa, JognaKhera, Hulas and Kunal), belonging to theHarappan civilization and other contemporary cultures provided a new suit of data on quantitativeestimate of the hydroclimatic condition (specifically relative humidity) and water availabilityduring the existence of this civilization

Rice grows in saturated soil water condition and its requirement for water is highest amongst other cereal crops. In India, the southwest monsoon wind regime brings rainfall that provides a favourable environment for rice cultivation. Thus, there is significant dependency ofrice production on the southwest monsoon rainfall. Being a crop that grows across diverse climatic regions in India ranging from the humid to semi-arid, it offers possibility to explore therelationship between stable isotopic compositions in the grain organic matter with the climaticfactors relevant for its growth. In this thesis, we measured the isotopic compositions of oxygen, hydrogen and carbon of several rice genotypes that were cultivated during the southwest monsoon in diverse climatic regions across the Indian landmass. These isotopic values were then compared with the seasonalaverage values of climate factors such as relative humidity and temperature. Together with thiswe also studied the dependency of the oxygen isotope composition of the grain OM (δ18OOM) onthat of the source water (δ18OSW). Upon removal of δ18OSW effect from δ18OOM, we obtained astrong and significant relationship between the 18O enrichment in grain organic matter (definedas 18OOM) with relative humidity. The gradient recorded was 0.45‰ shift in 18OOM with 1%change in the relative humidity level. This relationship can potentially be used to estimate thepast variations in relative humidity (and by extension, can provide a measure of monsoon rainfallvariations). We further validated this relationship based on experiments carried out in aglasshouse where all the physical factors were well-monitored. Together with this, carbonisotopic composition measured in the rice grain organic matter were used to infer the water useefficiency of rice grown in different climatic settings. The stable isotope approach was furtherimplemented for studying the archaeological rice grains recovered from archaeological sites. Analysis of carbon isotopic composition of archaeological rice grains from seven archaeologicalsites (Balu, Kanmer, Ojiyana, Lahuradewa, JognaKhera, Hulas and Kunal), belonging to theHarappan civilization and other contemporary cultures provided a new suit of data on quantitativeestimate of the hydroclimatic condition (specifically relative humidity) and water availabilityduring the existence of this civilization.

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The thesis presents observations on the CO2 concentration and carbon isotopes in air CO2 (δ13C) to constrain the inter-annual variability of carbon inventory over the Southern Ocean between the years 2011-2013. Based on the observation, the region of CO2 venting was identified over the Southern Ocean. Further, isotopic characterization allowed inferring about the possible sources of CO2 degassing and contribution from the dissolved inorganic carbon (DIC) that exsolved to generate CO2. It is concluded that the origin CO2 is mainly from the degassing of CO2 available from the dissociation of DIC or organic degradation. Live Foraminiferal samples of Globigerina bulloides from towing were captured, separated and analysed for δ18O and δ13C from various locations across the Southern Ocean between 10°N−60°S. A large similarities in the estimated values (deduced from simultaneous composition of ocean water 18O, δ13C in DIC and temperature i.e. SST under equilibrium condition) and measured δ18O and δ13C values were observed until 40°S from the equator, and hence it was concluded that the calcification depth of G. bulloides is confined to a depth of ~75-200m till 40°S latitude. However, further south (>40oS) disequilibrium from the estimates was detected. A number of possible reasons were cited for the observed disequilibrium such as (1) Deeper depth habitat (2) Partial dissolution (3) Non-equilibrium calcification (4) Oceanic Suess Effect and (5) Genetic Variability. A box model of isotopic mass balance was presented in this study to explain the pattern of enrichment in the 13C values of sea water DIC with latitude (up to about 43°S). The model shows that a steady state of the carbon isotope ratio of water is achieved in a relatively short time of ~5000 days. Rainwater isotope in the open marine condition across the latitudinal transects over Southern Ocean marking zone of precipitation and evaporation is another element of this thesis. A variation with excess lighter isotopes in rainwater was observed in high latitude rain in this study. Observed isotopic depletion is attributed to rainout process over the ocean. The average rainout fraction over the Southern Ocean in the region of zone of precipitation is ~44%, while it drops to ~25% in the zone of evaporation. Second part of the thesis presents a novel method of isotope thermometry which is called “clumped isotope (13C18O16O16O-2 in the calcite structure) thermometry”. A revision in the thermometry equation relating 47 vs T in synthetic carbonates precipitates and otoliths was proposed. The revised calibration was used on fish otoliths from the modern and past environment to estimate the temperatures. Together with the clumped isotope, conventional stable isotopes in the shell carbonates were measured to effectively reconstruct the seasonal fresh water fraction at seasonal time scales.