Biosynthesis of barley wax ß-diketones: a type-III polyketide synthase condensing two fatty acyl units.

The surface coatings of cereal plants are dominated by waxy ß-diketones crucial for drought resistance and, therefore, grain yield. Here, barley (Hordeum vulgare) wax analyses reveal ß-diketone and associated 2-alkanol ester profiles suggesting a common C16 3-ketoacid precursor. Isotope analysis further shows that the major (C31) diketone is synthesized from two plastidial C16 acyl units. Previous studies identified a gene cluster encoding enzymes responsible for ß-diketone formation in barley, but left their biochemical functions unknown. Various assays now characterize one of these enzymes as a thioesterase producing long-chain (mainly C16) 3-ketoacids, and another one as a polyketide synthase (PKS) condensing the 3-ketoacids with long-chain (mainly C16) acyl-CoAs into ß-diketones. The two enzymes are localized to the plastids and Endoplasmic Reticulum (ER), respectively, implying substrate transfer between these two sub-cellular compartments. Overall, our findings define a two-step pathway involving an unprecedented PKS reaction leading directly to the ß-diketone products.

A Pliocene Precipitation Isotope Proxy-Model Comparison Assessing the Hydrological Fingerprints of Sea Surface Temperature Gradients.

The Pliocene offers insights into future climate, with near-modern atmospheric pCO2 and global mean surface temperature estimated to be 3-4°C above pre-industrial. However, the hydrological response differs between future global warming and early Pliocene climate model simulations. This discrepancy results from the use of reduced meridional and zonal sea surface temperature (SST) gradients, based on foraminiferal Mg/Ca and Alkenone proxy evidence, to force the early Pliocene simulation. Subsequent, SST reconstructions based on the organic proxy TEX86, have found warmer temperatures in the warm pool, bringing the magnitude of the gradient reductions into dispute. We design an independent test of Pliocene SST scenarios and their hydrological cycle "fingerprints." We use an isotope-enabled General Circulation Model, iCAM5, to model the distribution of water isotopes in precipitation in response to four climatological SST and sea-ice fields representing modern, abrupt 4 × CO2, late Pliocene and early Pliocene climates. We conduct a proxy-model comparison with all the available precipitation isotope proxy data, and we identify target regions that carry precipitation isotopic fingerprints of SST gradients as priorities for additional proxy reconstructions. We identify two regions with distinct precipitation isotope (D/H) fingerprints resulting from reduced SST gradients: the Maritime Continent (D-enriched due to reduced convective rainfall) and the Sahel (wetter, more deep convection, D-depleted). The proxy-model comparison using available plant wax reconstructions, mostly from Africa, is promising but inconclusive. Additional proxy reconstructions are needed in both target regions and in much of the world for significant tests of SST scenarios and dynamical linkages to the hydrological cycle.

Crop breeding has increased the productivity and leaf wax n-alkane concentration in a series of five winter wheat cultivars developed over the last 60 years.

Plant wax n-alkanes are a major constituent of the leaf and grain surface. In this study, we explored what can be learned from the abundance and carbon isotopic composition (δ13C) of n-alkanes in historical winter wheat cultivars. We investigated leaf and grain wax n-alkane concentration (ΣalkLand ΣalkG) and carbon isotopes (δ13CalkL and δ13CalkG) on C29 as well as bulk leaf and grain carbon isotopes (δ13CbulkL and δ13CbulkG) to assess if these wax components changed across five wheat cultivars released from the 1950s to the early 2010s. Results showed that ΣalkL and grain yield increased, while δ13CalkL and δ13CbulkL decreased across the historical wheat cultivars. We found a significant correlation between ΣalkL and shoot biomass at the early growth stage, and a strong correlation between ΣalkL at the grain-filling stage and grain yield. Grain measures, including ΣalkG, δ13CalkG, and δ13CbulkG did not correlate with crop production. Although δ13CalkL and grain yield were not correlated at the flowering stage, they were correlated at the grain-filling stage under dry conditions. Our results indicate that increased ΣalkL has been indirectly selected in breeding efforts to improve crop production in winter wheat, suggesting that greater leaf waxiness confers advantages for crop growth.

Sustained wood burial in the Bengal Fan over the last 19 My.

The Ganges-Brahmaputra (G-B) River system transports over a billion tons of sediment every year from the Himalayan Mountains to the Bay of Bengal and has built the world's largest active sedimentary deposit, the Bengal Fan. High sedimentation rates drive exceptional organic matter preservation that represents a long-term sink for atmospheric CO2 While much attention has been paid to organic-rich fine sediments, coarse sediments have generally been overlooked as a locus of organic carbon (OC) burial. However, International Ocean Discovery Program Expedition 354 recently discovered abundant woody debris (millimeter- to centimeter-sized fragments) preserved within the coarse sediment layers of turbidite beds recovered from 6 marine drill sites along a transect across the Bengal Fan (∼8°N, ∼3,700-m water depth) with recovery spanning 19 My. Analysis of bulk wood and lignin finds mostly lowland origins of wood delivered episodically. In the last 5 My, export included C4 plants, implying that coarse woody, lowland export continued after C4 grassland expansion, albeit in reduced amounts. Substantial export of coarse woody debris in the last 1 My included one wood-rich deposit (∼0.05 Ma) that encompassed coniferous wood transported from the headwaters. In coarse layers, we found on average 0.16 weight % OC, which is half the typical biospheric OC content of sediments exported by the modern G-B Rivers. Wood burial estimates are hampered by poor drilling recovery of sands. However, high-magnitude, low-frequency wood export events are shown to be a key mechanism for C burial in turbidites.

Age and context of mid-Pliocene hominin cranium from Woranso-Mille, Ethiopia.

A fossil hominin cranium was discovered in mid-Pliocene deltaic strata in the Godaya Valley of the northwestern Woranso-Mille study area in Ethiopia. Here we show that analyses of chemically correlated volcanic layers and the palaeomagnetic stratigraphy, combined with Bayesian modelling of dated tuffs, yield an age range of 3.804 ± 0.013 to 3.777 ± 0.014 million years old (mean ± 1σ) for the deltaic strata and the fossils that they contain. We also document deposits of a perennial lake beneath the deltaic sequence. Mammalian fossils associated with the cranium represent taxa that were widespread at the time and data from botanical remains indicate that the vegetation in the lake and delta catchment was predominantly dry shrubland with varying proportions of grassland, wetland and riparian forest. In addition, we report high rates of sediment accumulation and depositional features that are typical of a steep topographic relief and differ from younger Woranso-Mille fossil localities, reflecting the influence of active rift processes on the palaeolandscape.

Comparison of three methods for the methylation of aliphatic and aromatic compounds.

RATIONALE: Methylation protocols commonly call for acidic, hot conditions that are known to promote organic 1 H/2 H exchange in aromatic and aliphatic C-H bonds. Here we tested two such commonly used methods and compared a third that avoids these acidic conditions, to quantify isotope effects with each method and to directly determine acidic-exchange rates relevant to experimental conditions. METHODS: We compared acidic and non-acidic methylation approaches catalyzed by hydrochloric acid, acetyl chloride and EDCI (1-ethyl-3-(3-dimethylaminopropyl)carbodiimide)/DMAP (4-dimethylaminopyridine), respectively. These were applied to two analytes: phthalic acid (an aromatic) and octacosanoic acid (an aliphatic). We analyzed yield by gas chromatography/flame ionization (GC/FID) and hydrogen and carbon isotopic compositions by isotope ratio mass spectrometry (GC/IRMS). We quantified the 1 H/2 H exchange rate on dimethyl phthalate under acidic conditions with proton nuclear magnetic resonance (1 H-NMR) measurements. RESULTS: The δ2 H and δ13 C values and yield were equivalent among the three methods for methyl octacosanoate. The two acidic methods resulted in comparable yield and isotopic composition of dimethyl phthalate; however, the non-acidic method resulted in lower δ2 H and δ13 C values perhaps due to low yields. Concerns over acid-catalyzed 1 H/2 H exchange are unwarranted as the effect was trivial over a 12-h reaction time. CONCLUSIONS: We find product isolation yield and evaporation to be the main concerns in the accurate determination of isotopic composition. 1 H/2 H exchange reactions are too slow to cause measurable isotope fractionation over the typical duration and reaction conditions used in methylation. Thus, we are able to recommend continued use of acidic catalysts in such methylation reactions for both aliphatic and aromatic compounds.

Hydroclimate of the western Indo-Pacific Warm Pool during the past 24,000 years.

The Indo-Pacific Warm Pool (IPWP) is a key site for the global hydrologic cycle, and modern observations indicate that both the Indian Ocean Zonal Mode (IOZM) and the El Niño Southern Oscillation exert strong influence on its regional hydrologic characteristics. Detailed insight into the natural range of IPWP dynamics and underlying climate mechanisms is, however, limited by the spatial and temporal coverage of climate data. In particular, long-term (multimillennial) precipitation patterns of the western IPWP, a key location for IOZM dynamics, are poorly understood. To help rectify this, we have reconstructed rainfall changes over Northwest Sumatra (western IPWP, Indian Ocean) throughout the past 24,000 y based on the stable hydrogen and carbon isotopic compositions (δD and δ(13)C, respectively) of terrestrial plant waxes. As a general feature of western IPWP hydrology, our data suggest similar rainfall amounts during the Last Glacial Maximum and the Holocene, contradicting previous claims that precipitation increased across the IPWP in response to deglacial changes in sea level and/or the position of the Intertropical Convergence Zone. We attribute this discrepancy to regional differences in topography and different responses to glacioeustatically forced changes in coastline position within the continental IPWP. During the Holocene, our data indicate considerable variations in rainfall amount. Comparison of our isotope time series to paleoclimate records from the Indian Ocean realm reveals previously unrecognized fluctuations of the Indian Ocean precipitation dipole during the Holocene, indicating that oscillations of the IOZM mean state have been a constituent of western IPWP rainfall over the past ten thousand years.

Analytical challenges in the quantitative determination of 2H/1H ratios of methyl iodide.

RATIONALE: A published method to determine the hydrogen isotope ((2)H/(1)H) ratios of methoxyl groups, cleaved from lignin by hydroiodic acid (HI), calls for the analysis of methyl iodide (CH(3)I). However, analysis of halogenated compounds by gas chromatography/pyrolysis/isotope ratio mass spectrometry (GC/P/IRMS) yields incomplete conversion into H(2) and unwanted HX products post-pyrolysis. METHODS: We tested analytical capabilities when measuring a pure CH(3) I standard using a GC Isolink pyrolysis furnace at 1420 °C and a DELTA V(Plus) ™ isotope ratio mass spectrometer, both by Thermo Scientific. We added and tested the efficacy of either a secondary reduction furnace containing heated metals or a cold trap to eliminate unwanted HI prior to IRMS analysis for (2)H/(1) H determinations. RESULTS: While 94% of the hydrogen in CH(3) I is converted into H(2) in GC/P/IRMS, 6% yields HI. The use of either a secondary reduction furnace or cold trap can eliminate HI. However, secondary reduction is untenable given changes in reduction/transmission efficiency and (2)H/(1) H drift. A cold trap provides a pragmatic solution: the δ(2)H values of -97 ‰ were measured from injections of 23-57 µg of CH(3)I to a precision of 4.5 ‰ (n = 26), within the error of the offline measurements. CONCLUSIONS: We have refined an earlier method to measure the δ(2)H values of CH(3)I by GC/P/IRMS by adding a cold trap to remove HI. This approach should facilitate future experimentation with the measurement of CH(3)I liberated from natural samples for potentially diverse applications including forensic sourcing of wood and tree-wood-based reconstructions of source water.