SNAr displacement reactions of 6-cyclohexylmethoxy-2-fluoropurine, 6-amino-2-butylsulfonyl-4-cyclohexylmethoxypyrimidine and 2-amino-6-chloropurine with substituted anilines (e.g. the weakly nucleophilic 4-aminobenzenesulfonamide) are dramaticallyaccelerated in the presence of trifluoroacetic acid and occur especially efficiently in 2,2,2-trifluoroethanol solvent.
Rationale:The use of multi-isotopic analysis (δ 15 N, δ 13 C and δ 34 S values) of archaeological bone collagen to assist in the interpretation of diet, movement and mobility of prehistoric populations is gradually increasing, yet many researchers have traditionally avoided investigating sulphur due to its very low concentrations (<0.3%) in mammalian collagen. For this reason, and as a consequence of analytical detection limits, sulphur is usually measured separately from carbon and nitrogen, which leads to longer analytical times and higher costs.
Methods:A Thermo Scientific™ EA IsoLink™ isotope ratio mass spectrometry (IRMS) system, with the ability to rapidly heat a gas chromatography (GC) column and concentrate the sample gas online without cryo-trapping, was used at the Radiocarbon Laboratory at the Scottish Universities Environmental Research Centre (SUERC). Optimisation of the GC temperature and carrier gas flow rate in the elemental analyser resulted in improved signal-to-noise (S/N) ratio and sensitivity for SO 2 . This allowed for routine sequential N 2 , CO 2 and SO 2 measurements on small samples of bone collagen.Results: Improvements in sample gas transfer to the mass spectrometer allows for sequential δ 15 N, δ 13 C and δ 34 S values to be measured in 1-1.5 mg samples of bone collagen. Moreover, the sensitivity and S/N ratio of the sample gas, especially SO 2 , is improved, resulting in precisions of ±0.15‰ for δ 15 N values, ±0.1‰ for δ 13 C values and ±0.3‰ for δ 34 S values. Previous instrumentation allowed for the analysis of~30 unknown samples before undertaking maintenance; however, 150 unknown samples can now be measured, meaning a 5-fold increase in sample throughput.
Conclusions:The ability to sequentially measure δ 15 N, δ 13 C and δ 34 S values rapidly in archaeological bone collagen is an attractive option to researchers who want to build larger, more succinct datasets for their sites of interest, at a much-reduced analytical cost and without destroying larger quantities of archaeological material.
ABSTRACT. Stable isotope ratios of carbon, nitrogen, and sulfur in human bone collagen are used routinely to aid in the reconstruction of ancient diets. Isotopic analysis of human remains from sites in the Iron Gates section of the Lower Danube Valley has led to conflicting interpretations of Mesolithic diets in this key region of southeast Europe. One view (Bonsall et al. 1997(Bonsall et al. , 2004) is that diets were based mainly on riverine resources throughout the Mesolithic. A competing hypothesis (Nehlich et al. 2010) argues that Mesolithic diets were more varied with at least one Early Mesolithic site showing an emphasis on terrestrial resources, and riverine resources only becoming dominant in the Later Mesolithic. The present article revisits this issue, discussing the stable isotope data in relation to archaeozoological and radiocarbon evidence.
This study provides an assessment of the temporal changes in ΔR, which is the local deviation from the global surface water marine reservoir effect (MRE), in the Point Barrow area of the Alaskan Arctic, a coastal archaeological area that has experienced severe erosion accelerated by global warming. A total of 26 samples were submitted for radiocarbon (14C) dating from eight secure Thule (AD 1000–1750) archaeological contexts, and specifically from archaeological features with paired processed seal and caribou bones that had been frozenin situ. This new approach towards ΔR estimation provides a best-fit local correction for the14C dating of human populations by focusing on the marine mammal (seals) predominantly consumed by the Thule (Coltrain et al. 2016). The weighted-mean ΔR value on these pairs is 450 ± 84 yr, which is about 50 years less than the weighted-mean (506 ± 69 yr) for the Point Barrow area calculated through14C measurements from four known-age bivalves collected in AD 1913 (McNeely et al. 2006). The effects of using this new ΔR value for calibration was assessed through the Bayesian chronological modeling of 5414C measurements from samples of human skeletons interred in the Nuvuk cemetery at Point Barrow, the largest ancient cemetery in northwest Alaska and traditionally thought to date to the Thule and earlier Birnirk (AD 500–1000) periods.
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