Performance of induction module cavity ring-down spectroscopy (IM-CRDS) for measuring δ18 O and δ2 H values of soil, stem, and leaf waters.

RATIONALE: Induction module cavity ring-down spectroscopy (IM-CRDS) has been proposed as a rapid and cost-effective alternative to cryogenic vacuum distillation (CVD) and isotope ratio mass spectrometry (IRMS) for the measurement of δ18 O and δ2 H values in matrix-bound waters. In the current study, we characterized the performance of IM-CRDS relative to CVD and IRMS and investigated the mechanisms responsible for differences between the methods. METHODS: We collected a set of 75 soil, stem, and leaf water samples, and measured the δ18 O and δ2 H values of each sample with four techniques: CVD and IRMS, CVD and CRDS, CVD and IM-CRDS, and IM-CRDS alone. We then calculated the isotopic errors for each of the three CRDS methods relative to CVD and IRMS, and analyzed the relationships among these errors and suites of diagnostic spectral parameters that are indicative of organic contamination. RESULTS: The IM-CRDS technique accurately assessed the δ18 O and δ2 H values of pure waters, but exhibited progressively increasing errors for soil waters, stem waters, and leaf waters. For soils, the errors were attributable to subsampling of isotopically heterogeneous source material, whereas for stems and leaves, they were attributable to spectral interference. Unexpectedly, the magnitude of spectral interference was higher for the solid samples analyzed directly via IM-CRDS than for those originally extracted via CVD and then analyzed by IM-CRDS. CONCLUSIONS: There are many types of matrix-bound water samples for which IM-CRDS measurements include significant errors from spectral interference. As a result, spectral analysis and validation should be incorporated into IM-CRDS post-processing procedures. In the future, IM-CRDS performance could be improved through: (i) identification of the compounds that cause spectral interference, and either (ii) modification of the combustion step to completely oxidize these compounds to CO2 , and/or (iii) incorporation of corrections for these compounds into the spectral fitting models used by the CRDS analyzers. Copyright © 2016 John Wiley & Sons, Ltd.

Otolith-temperature estimates in Atlantic bluefin tuna (Thunnus thynnus) from the Mediterranean Sea: Insights from clumped isotope measurements.

The subpopulation and/or contingent structure of Atlantic bluefin tuna (Thunnus thynnus) within the Mediterranean Sea is undefined, leading to uncertainty regarding the best strategy for an effective assessment and management of this highly exploited stock. This study aimed to reconstruct temperatures experienced by Atlantic bluefin tuna during the early life period (<3.5 months) using clumped isotope temperature proxy, an innovative geothermometer for carbonates, that does not require previous knowledge of other environmental parameters such as water oxygen composition. We examined otolith chemistry in fish captured from 3 different areas of the Mediterranean Sea and adjacent waters. We found that mean seasonal temperature estimates from clumped isotopes did not differ significantly from satellite derived and otolith oxygen stable isotopic ratios derived temperatures, except for the central Mediterranean Sea, were clumped isotopes derived temperatures were significantly higher than satellite derived temperatures. However, the sensitivity of the clumped isotope thermometer was found to be lower than that based on oxygen fractionation equation, with high variance observed in the clumped isotopes derived temperature estimates. We also observed that clumped isotope derived temperatures were undistinguishable among bluefin tuna captured in the Gibraltar Strait, the central, and eastern Mediterranean Sea. In this paper, we discuss the major sources of uncertainty in temperature reconstructions using bluefin tuna otoliths.

Age-growth relationships, temperature sensitivity and palaeoclimate-archive potential of the threatened Altiplano cactus Echinopsis atacamensis.

The tall (>4 m), charismatic and threatened columnar cacti, pasacana [Echinopsis atacamensis (Vaupel) Friedrich & G.D. Rowley)], grows on the Bolivian Altiplano and provides environmental and economic value to these extremely cold, arid and high-elevation (~4000 m) ecosystems. Yet very little is known about their growth rates, ages, demography and climate sensitivity. Using radiocarbon in spine dating time series, we quantitatively estimate the growth rate (5.8 and 8.3 cm yr-1) and age of these cacti (up to 430 years). These data and our field measurements yield a survivorship curve that suggests precipitation on the Altiplano is important for this species' recruitment. Our results also reveal a relationship between nighttime temperatures on the Altiplano and the variation in oxygen isotope values in spines (δ18O). The annual δ18O minimums from 58 years of in-series spine tissue from pasacana on the Altiplano provides at least decadal proxy records of temperature (r = 0.58; P < 0.0001), and evidence suggests that there are longer records connecting modern Altiplano temperatures to sea-surface temperatures (SSTs) in the Atlantic Ocean. While the role of Atlantic SSTs on the South American Summer Monsoon (SASM) and precipitation on the Bolivian Altiplano is well described, the impact of SSTs on Altiplano temperatures is disputed. Understanding the modern impact of SSTs on temperature on the Altiplano is important to both understand the impact of future climate change on pasacana cactus and to understand past climate changes on the Altiplano. This is the best quantitative evidence to date of one of the oldest known cactus in the world, although there are likely many older cacti on the Altiplano, or elsewhere, that have not been sampled yet. Together with growth, isotope and age data, this information should lead to better management and conservation outcomes for this threatened species and the Altiplano ecosystem.

Atlantic forcing of persistent drought in West Africa.

Although persistent drought in West Africa is well documented from the instrumental record and has been primarily attributed to changing Atlantic sea surface temperatures, little is known about the length, severity, and origin of drought before the 20th century. We combined geomorphic, isotopic, and geochemical evidence from the sediments of Lake Bosumtwi, Ghana, to reconstruct natural variability in the African monsoon over the past three millennia. We find that intervals of severe drought lasting for periods ranging from decades to centuries are characteristic of the monsoon and are linked to natural variations in Atlantic temperatures. Thus the severe drought of recent decades is not anomalous in the context of the past three millennia, indicating that the monsoon is capable of longer and more severe future droughts.