Isotopic analysis of otolith carbonates using laser heating: A fast method for obtaining high-resolution climate signal.

RATIONALE: The stable isotopic compositions of biogenic carbonates like fish otoliths (ear bones) are widely used for palaeoclimatic reconstruction. The conventional method using acid-digestion of micro-milled samples is a multi-step time-consuming process. Here we report a fast method based on laser heating of otolith carbonates to obtain accurate and high-resolution stable isotopic compositions. METHOD: Otoliths of catfish from the Gulf of Kutch were analysed to check the precision, accuracy and time-resolution of the isotope ratios. The CO2 , generated by heating otoliths with a 50 W CO2 laser, was analysed for its oxygen and carbon isotope ratio [δ18 O and δ13 C, with precision: 0.12 and 0.17‰ (1σ), accuracy: 0.13 and 0.25‰, respectively] using a continuous-flow isotope ratio mass spectrometer. The effect of laser power (0.7-2 W) was assessed for reproducible data. Samples were roasted and analysed to account for the effect of the inherent organic matter on the isotopic values. RESULTS: Roasting did not alter the δ18 O of the otoliths but increased the δ13 C slightly. High-resolution (125 µm) analysis of the right and left otolith of a fish yielded similar δ18 O and δ13 C values, suggesting the suitability of either of them for deriving the climate signal. An increase in δ18 O values from ~ -2‰ to ~ -1‰, observed across the ontogeny, is consistent with the known migratory behaviour of the catfish between freshwater and the sea. CONCLUSIONS: The otolith δ18 O value of an adult fish records the sea surface temperature (with ~3°C uncertainty) on a monthly scale. The otolith δ13 C values, with the knowledge of dietary δ13 C, provide the mean annual δ13 C value of dissolved inorganic carbon. The study provides a rapid method for retrieving high-resolution seasonal climate data from otoliths found aplenty in geological/archaeological records.

A simple cryogenic method for efficient analysis of triple oxygen isotopes in silicates.

RATIONALE: Oxygen isotopic ratios of silicates are excellent tools to reconstruct paleotemperature and isotopic composition of the precipitating fluid. However, the measurement of 17 O/16 O is difficult due to the low abundance of 17 O. The present study reports a simplified high-precision analytical technique for measuring the two oxygen isotope ratios, 17 O/16 O and 18 O/16 O, in silicates. METHODS: Silicate samples were ablated by a CO2 laser in a BrF5 environment. The released oxygen (O2 ) was then cryogenically trapped in a molecular sieve zeolite (MSZ). Associated contaminants such as BrF5 , F2 , NF3 etc. were cleaned by passing the gas through a NaCl trap followed by a cooled (-25°C) MSZ-packed U-tube trap. The purified O2 was analysed in a MAT 253 isotope ratio mass spectrometer for oxygen isotope ratios. RESULTS: The δδ17 O and δ18 O values of the working gas were calibrated by NBS-28 and crosschecked by inter-laboratory references UWG-2, SCO and IMAU-O2 . The average analytical precisions (using aliquots of NBS-28, UWG-2, SCO, and laboratory internal standards IIT-KGP-SQ quartz and IIT-KGP-NQ quartz) of the δ17 O, δ18 O and ∆'17 O values were 0.04‰, 0.08‰ and 4 per meg, respectively. CONCLUSIONS: A new cryogenic cleaning technique was developed that does not require GC but efficiently removes NF3 -contaminants from oxygen gas produced by laser fluorination of silicates. The technique is simple, quick and cost-effective and provides highly precise and accurate δ17 O, δ18 O and ∆'17 O values.