Characterization of the analytical performance of δ15 N and δ18 O measurements by the silver nitrate method in the framework of nitrate source apportioning.

RATIONALE: Nitrate pollution represents one of the most important issues for ground and surface water quality and source identification is essential for developing effective mitigation practices. Nitrate isotopic fingerprinting can be utilized to identify the sources of nitrate pollution in aquifers. However, it is crucial to assess the performances (precision and accuracy) of the analytical procedure applied to measure the δ15 N and δ18 O values of nitrates from field samples to correctly apply this tool. METHODS: Nitrates were extracted from a large number of KNO3 samples using the AgNO3 method, and the δ15 N and δ18 O values of these nitrate extracts were measured by isotope ratio mass spectrometry. The availability of this dataset, comprising 693 unprocessed quality control (QC) KNO3 samples and 618 processed samples, allowed us to rigorously quantify the performance of the procedures employed. A salt doping experiment was also performed from which the effects of contaminants on the performance of the method could be ascertained. RESULTS: The overall instrumental reproducibility for the analysis of unprocessed QC samples was 0.5‰ and 2‰ for δ15 N and δ18 O values, respectively, and a strict dependence on signal amplitude was observed. No isotope fractionation was reported for reference samples that were processed according to the "identical treatment" principle (ITP) but normalized by unprocessed reference materials. A significant increase in the standard deviation (SD) was, however, observed compared with that for unprocessed samples. The SD of the processed QC samples allowed us to quantify the reproducibility of the entire procedure as 0.6‰ and 1.0‰ for δ15 N and δ18 O values, respectively. This was comparable with the system reproducibility when normalization using processed reference materials was applied according to the ITP. CONCLUSIONS: Normalization with processed standards is essential to achieve high-precision measurements of the δ15 N and δ18 O values of nitrates extracted from unknown samples. This procedure allowed good accuracy to be guaranteed, and precision levels comparable with the observed instrumental performance to be achieved. A salt doping experiment showed a significant influence of the SO4 2- content on the δ15 N values.

Early Last Interglacial ocean warming drove substantial ice mass loss from Antarctica.

The future response of the Antarctic ice sheet to rising temperatures remains highly uncertain. A useful period for assessing the sensitivity of Antarctica to warming is the Last Interglacial (LIG) (129 to 116 ky), which experienced warmer polar temperatures and higher global mean sea level (GMSL) (+6 to 9 m) relative to present day. LIG sea level cannot be fully explained by Greenland Ice Sheet melt (∼2 m), ocean thermal expansion, and melting mountain glaciers (∼1 m), suggesting substantial Antarctic mass loss was initiated by warming of Southern Ocean waters, resulting from a weakening Atlantic meridional overturning circulation in response to North Atlantic surface freshening. Here, we report a blue-ice record of ice sheet and environmental change from the Weddell Sea Embayment at the periphery of the marine-based West Antarctic Ice Sheet (WAIS), which is underlain by major methane hydrate reserves. Constrained by a widespread volcanic horizon and supported by ancient microbial DNA analyses, we provide evidence for substantial mass loss across the Weddell Sea Embayment during the LIG, most likely driven by ocean warming and associated with destabilization of subglacial hydrates. Ice sheet modeling supports this interpretation and suggests that millennial-scale warming of the Southern Ocean could have triggered a multimeter rise in global sea levels. Our data indicate that Antarctica is highly vulnerable to projected increases in ocean temperatures and may drive ice-climate feedbacks that further amplify warming.

Measurement of δ13C values of soil amino acids by GC-C-IRMS using trimethylsilylation: a critical assessment.

In this study, we evaluated trimethylsilyl (TMS) derivatives as derivatization reagents for the compound-specific stable carbon isotope analysis of soil amino acids by gas chromatography-combustion-isotope ratio mass spectrometry (GC-C-IRMS). We used non-proteinogenic amino acids to show that the extraction-derivatization-analysis procedure provides a reliable method to measure δ(13)C values of amino acids extracted from soil. However, we found a number of drawbacks that significantly increase the final total uncertainty. These include the following: production of multiple peaks for each amino acid, identified as di-, tri- and tetra-TMS derivatives; a number of TMS-carbon (TMS-C) atoms added lower than the stoichiometric one, possibly due to incomplete combustion; different TMS-C δ(13)C for di-, tri- and tetra-TMS derivatives. For soil samples, only four amino acids (leucine, valine, threonine and serine) provide reliable δ(13)C values with a total average uncertainty of 1.3 ‰. We conclude that trimethylsilyl derivatives are only suitable for determining the (13)C incorporation in amino acids within experiments using (13)C-labelled tracers but cannot be applied for amino acids with natural carbon isotope abundance until the drawbacks described here are overcome and the measured total uncertainty significantly decreased.

The privileged burial of the Pava Pieve (Siena, 8th Century AD).

RATIONALE: The 6(th) archaeological excavation campaign performed at the 'Pieve di Pava' (San Giovanni d'Asso, Siena, Italy) unearthed a privileged stone burial of a single individual (US 2378), covered by a monolithic slab and placed in front of an altar. The skeletal remains of a young male (18-20 years old), not in anatomical connection, were found at the bottom floor of a tomb (160 cm long, 40 cm large and over 70 cm deep). METHODS: A multidisciplinary study has been carried out concerning that privileged bone burial. The study combines paleopathology studies, stable isotope palaeodietary reconstruction, radiocarbon dating and archaeological analyses. RESULTS: (14) C dating of the skeleton revealed a date between 650 and 688 AD. Stable isotope analysis (δ(18) O, δ(13) C, δ(15) N) attested that he was probably a member of the local population, whose diet was rather rich in animal proteins. The paleopathological study diagnosed a case of acromesomelic dysplasia, a congenital anomaly with disproportion of the limbs. Archaeological evidence regarding the circular delimitation of the bones suggested that the skeleton was a secondary deposition, transported to the church in a sack. CONCLUSIONS: We argue that the relic was used for the re-consecration of the church, following the restoration work in the 8(th) century. We conclude that the skeleton belonged to an eminent personage (e.g., either the member of a local elite family or a saint).

An isotopic method for testing the influence of leaf litter quality on carbon fluxes during decomposition.

During microbial breakdown of leaf litter a fraction of the C lost by the litter is not released to the atmosphere as CO(2) but remains in the soil as microbial byproducts. The amount of this fraction and the factors influencing its size are not yet clearly known. We performed a laboratory experiment to quantify the flow of C from decaying litter into the soil, by means of stable C isotopes, and tested its dependence on litter chemical properties. Three sets of (13)C-depleted leaf litter (Liquidambar styraciflua L., Cercis canadensis L. and Pinus taeda L.) were incubated in the laboratory in jars containing (13)C-enriched soil (i.e. formed C4 vegetation). Four jars containing soil only were used as a control. Litter chemical properties were measured using thermogravimetry (Tg) and pyrolysis-gas chromatography/mass spectrometry-combustion interface-isotope ratio mass spectrometry (Py-GC/MS-C-IRMS). The respiration rates and the delta(13)C of the respired CO(2) were measured at regular intervals. After 8 months of incubation, soils incubated with both L. styraciflua and C. canadensis showed a significant change in delta(13)C (delta(13)C(final) = -20.2 +/- 0.4 per thousand and -19.5 +/- 0.5 per thousand, respectively) with respect to the initial value (delta(13)C(initial) = -17.7 +/- 0.3 per thousand); the same did not hold for soil incubated with P. taeda (delta(13)C(final:)-18.1 +/- 0.5 per thousand). The percentages of litter-derived C in soil over the total C loss were not statistically different from one litter species to another. This suggests that there is no dependence of the percentage of C input into the soil (over the total C loss) on litter quality and that the fractional loss of leaf litter C is dependent only on the microbial assimilation efficiency. The percentage of litter-derived C in soil was estimated to be 13 +/- 3% of total C loss.

Paleodiet characterisation of an Etrurian population of Pontecagnano (Italy) by Isotope Ratio Mass Spectrometry (IRMS) and Atomic Absorption Spectrometry (AAS)(#).

Human bones recovered from the archaeological site of Pontecagnano (Salerno, Italy) have been studied to reconstruct the diet of an Etrurian population. Two different areas were investigated, named Library and Sant' Antonio, with a total of 44 tombs containing human skeletal remains, ranging in age from the 8th to the 3rd century B.C. This time span was confirmed by 14C dating obtained using Accelerator Mass Spectrometry (AMS) on one bone sample from each site. Atomic Absorption Spectrometry (AAS) was used to extract information about the concentration of Sr, Zn, Ca elements in the bone inorganic fraction, whilst stable isotope ratio measurements (IRMS) were carried out on bone collagen to obtain the delta13C and delta15N. A reliable technique has been used to extract and separate the inorganic and organic fractions of the bone remains. Both IRMS and AAS results suggest a mixed diet including C3 plant food and herbivore animals, consistent with archaeological indications.

Sampling soil-derived CO2 for analysis of isotopic composition: a comparison of different techniques.

A new system for soil respiration measurement [P. Rochette, L.B. Flanagan, E.G. Gregorich. Separating soil respiration into plant and soil components using analyses of the natural abundance of carbon-13. Soil Sci. Soc. Am. J., 63, 1207-1213 (1999).] was modified in order to collect soil-derived CO2 for stable isotope analysis. The aim of this study was to assess the suitability of this modified soil respiration system to determine the isotopic composition (delta13C) of soil CO2 efflux and to measure, at the same time, the soil CO2 efflux rate, with the further advantage of collecting only one air sample. A comparison between different methods of air collection from the soil was carried out in a laboratory experiment. Our system, as well as the other dynamic chamber approach tested, appeared to sample the soil CO2, which is enriched with respect to the soil CO2 efflux, probably because of a mass dependent fractionation during diffusion and because of the atmospheric contribution in the upper soil layer. On the contrary, the static accumulation of CO2 into the chamber headspace allows sampling of delta13C-CO2 of soil CO2 efflux.