Enzymatically catalyzed CO2 -H2 O equilibration for oxygen isotope analyses of aqueous samples.

RATIONALE: The classic CO2 -H2 O equilibration method is a very popular technique for the measurement of the oxygen isotope composition of aqueous samples in stable isotope geochemistry. This study examined whether enzymatically controlled CO2 -H2 O equilibration by carbonic anhydrase (CA) could reduce the time for oxygen isotope equilibrium between CO2 and H2 O at 25°C. METHODS: Four types of aqueous samples containing CA were equilibrated with CO2 gases using a continuous flow isotope ratio mass spectrometer equipped with an automated gas sample collection device. We examined the effect of CA concentration in an aqueous sample, the influence of drying technique for the preparation of sample vials containing dried CA, the age of CA stock solution, and the ionic strength and the oxygen isotope composition of aqueous samples. RESULTS: CA rapidly catalyzed the oxygen isotope exchange between CO2 and H2 O and was unaffected by drying technique or stock solution age. Compared with aqueous samples with no CA or 0.2 µmolal CA, samples containing 4 µmolal CA significantly reduced the CO2 -H2 O equilibration time for deionized water and artificial seawater (ionic strength = ~0.6) from ~19 h and ~23 h to ~0.30 h and ~0.77 h, respectively at 25°C. CONCLUSIONS: This enzymatically catalyzed CO2 -H2 O equilibration method is time-efficient, cost-effective, requires no additional data correction procedure, and can be used for most commercially available CO2 -H2 O equilibration devices without any modification.

A new online technique for the simultaneous measurement of the δ13C value of dissolved inorganic carbon and the δ18O value of water from a single solution sample using continuous-flow isotope ratio mass spectrometry.

RATIONALE: The oxygen isotope study of water reservoirs (δ(18)OH2O values) and the carbon isotope study of dissolved inorganic carbon (δ(13)CDIC values) are powerful tools to decipher Earth's past and present environmental changes. This study presents a novel online analytical technique, namely the DIC evolved CO2 Gas Equilibration Method (DIC-CO2-GEM), in which the δ(18)OH2O and δ(13)CDIC values can be simultaneously determined from a single solution sample. METHODS: The DIC-CO2-GEM measures both δ(18)OH2O and δ(13)CDIC values concurrently by combining the fundamental principles of the classic CO2-H2O equilibration and gas evolution methods, respectively. Phosphoric acid is used to convert dissolved inorganic carbon in a solution sample of 0.2 mL into gaseous CO2, which is then equilibrated with the solution at 25 °C. The oxygen and carbon isotope compositions are subsequently determined via continuous-flow isotope ratio mass spectrometry from the single solution sample. RESULTS: Results obtained employing the DIC-CO2-GEM are in good agreement (<± 0.07‰ for δ(18)OH2O values and < < ± 0.1‰ for δ(13)CDIC values) with those acquired using each of the traditional techniques. For both oxygen and carbon isotope measurements, an addition of 0.01 mL phosphoric acid yields the most consistent results between our technique and the traditional methods. CONCLUSIONS: Devised to combine the traditional approaches independently assessing δ(18)OH2O and δ(13)CDIC values, the DIC-CO2-GEM is less complex and highly efficient. It preserves the modern precision requirements for oxygen (± 0.09‰) and carbon (± 0.18‰) isotope analyses while accurately measuring both parameters simultaneously. This innovative method generates an abundance of data while minimizing resources and is suitable for a variety of practical applications.

Isotopic evidence for age-related immigration to imperial Rome.

Oxygen stable isotope ratios (delta(18)O) have been determined in carbonate in paired first and third molar teeth from individuals (N = 61) who lived in the town of Portus Romae ("Portus") and who were buried in the necropolis of Isola Sacra (First to Third centuries AD) near Rome, Italy. We compare these analyses with data for deciduous teeth of modern Roman children. Approximately one-third of the archaeological sample has first molar (M1) values outside the modern range, implying a large rate of population turnover at that time, consistent with historical data. Delta (18)O(ap) values suggest that a group within the sample migrated to the area before the third molar (M3) crown had completely formed (i.e., between 10 and 17.5 years of age). This is the first quantitative assessment of population mobility in Classical antiquity. This study demonstrates that migration was not limited to predominantly single adult males, as suggested by historical sources, but rather a complex phenomenon involving families. We hypothesize that migrants most likely came from higher elevations to the East and North of Rome. One individual with a higher delta(18)O value may have come (as a child) from an area isotopically similar to North Africa.

A preliminary analysis of the DNA and diet of the extinct Beothuk: a systematic approach to ancient human DNA.

We have used a systematic protocol for extracting, quantitating, sexing and validating ancient human mitochondrial and nuclear DNA of one male and one female Beothuk, a Native American population from Newfoundland, which became extinct approximately 180 years ago. They carried mtDNA haplotypes, which fall within haplogroups X and C, consistent with Northeastern Native populations today. In addition we have sexed the male using a novel-sexing assay and confirmed the authenticity of his Y chromosome with the presence of the Native American specific Y-QM3 single nucleotide polymorphism (SNP). This is the first ancient nuclear SNP typed from a Native population in the Americas. In addition, using the same teeth we conducted a stable isotopes analysis of collagen and dentine to show that both individuals relied on marine sources (fresh and salt water fish, seals) with no hierarchy seen between them, and that their water sources were pooled or stored water. Both mtDNA sequence data and Y SNP data hint at possible gene flow or a common ancestral population for both the Beothuk and the current day Mikmaq, but more importantly the data do not lend credence to the proposed idea that the Beothuk (specifically, Nonosabasut) were of admixed (European-Native American) descent. We also analyzed patterns of DNA damage in the clones of authentic mtDNA sequences; there is no tendency for DNA damage to occur preferentially at previously defined mutational hotspots, suggesting that such mutational hotspots are not hypervariable because they are more prone to damage.