An archaeobotanical and stable isotope approach to changing agricultural practices in the NW Mediterranean region around 4000 BC.

It has recently been observed, that a change in the crop spectrum happened during the so-called Middle Neolithic in France at ca. 4000 BC. An agricultural system based on free-threshing cereals (naked wheat and naked barley) seems to shift to one based on glume wheats. This is a major change for traditional farmers and this paper aims to shed light on its possible causes. Here we describe the results of new investigations in a key area for the understanding of this process: the NW Mediterranean arch, where free-threshing cereals are the main cultivars since ca. 5100 BC. New data confirm that the shift towards glume wheats is also observed in some sites of the NE of the Iberian Peninsula and that among the glume wheats that spread at ca. 4000 BC we should not only consider emmer and einkorn but also Timopheevi's wheat. Stable isotope analyses indicate no major decrease in soil fertility or alterations in local precipitation regimes. The agricultural change may be the result of a combination of the spread of damaging pests for free-threshing cereals and presumably new networks being developed with the North-eastern part of Italy and the Balkans.

In-situ experiment reveals CO2 enriched fluid migration in faulted caprock.

The sealing characteristics of the geological formation located above a CO2 storage reservoir, the so-called caprock, are essential to ensure efficient geological carbon storage. If CO2 were to leak through the caprock, temporal changes in fluid geochemistry can reveal fundamental information on migration mechanisms and induced fluid-rock interactions. Here, we present the results from a unique in-situ injection experiment, where CO2-enriched fluid was continuously injected in a faulted caprock analogue. Our results show that the CO2 migration follows complex pathways within the fault structure. The joint analysis of noble gases, ion concentrations and carbon isotopes allow us to quantify mixing between injected CO2-enriched fluid and resident formation water and to describe the temporal evolution of water-rock interaction processes. The results presented here are a crucial complement to the geophysical monitoring at the fracture scale highlighting a unique migration of CO2 in fault zones.

Biodegradation of poly(butylene succinate) in soil laboratory incubations assessed by stable carbon isotope labelling.

Using biodegradable instead of conventional plastics in agricultural applications promises to help overcome plastic pollution of agricultural soils. However, analytical limitations impede our understanding of plastic biodegradation in soils. Utilizing stable carbon isotope (13C-)labelled poly(butylene succinate) (PBS), a synthetic polyester, we herein present an analytical approach to continuously quantify PBS mineralization to 13CO2 during soil incubations and, thereafter, to determine non-mineralized PBS-derived 13C remaining in the soil. We demonstrate extensive PBS mineralization (65 % of added 13C) and a closed mass balance on PBS-13C over 425 days of incubation. Extraction of residual PBS from soils combined with kinetic modeling of the biodegradation data and results from monomer (i.e., butanediol and succinate) mineralization experiments suggest that PBS hydrolytic breakdown controlled the overall PBS biodegradation rate. Beyond PBS biodegradation in soil, the presented methodology is broadly applicable to investigate biodegradation of other biodegradable polymers in various receiving environments.

Archaeobotanical and isotopic analyses of waterlogged remains from the Neolithic pile-dwelling site of Zug-Riedmatt (Switzerland): Resilience strategies of a plant economy in a changing local environment.

The excellent preservation of the waterlogged botanical remains of the multiphase Neolithic pile-dwelling site of Zug-Riedmatt (Central Switzerland) yielded an ideal dataset to delve into the issue of plant economy of a community spanning several decades. The study identified a major change in crops where oil plants played a key role in the site's initial phase before being supplanted over the course of a few decades by naked wheat, barley and pea. Wild plants continued to be gathered albeit in different proportions. In the latest settlement phase, the changes in the local vegetation and in the values of the analyses of carbon stable isotopes suggest a less humid environment. The hypothesis is that the changes perceived in the plant economy represent a resilience strategy adopted by the inhabitants in reaction to short term local climatic alterations. The two types of soil sampling techniques (monolith and bulk) allowed comparing these results. While the density of plant remains appears to be underestimated among the samples collected by the monolith technique, the proportions of economic taxa remain unaffected. The findings thus reveal that when the bulk samplings are distributed carefully throughout multiphase sites and avoid mixing stratigraphical units, and if the samplings are representative of all archaeological features from a whole area, then each of the two techniques offer analogous results.

Reducing Uncertainties in Carbonate Clumped Isotope Analysis Through Consistent Carbonate-Based Standardization.

About a decade after its introduction, the field of carbonate clumped isotope thermometry is rapidly expanding because of the large number of possible applications and its potential to solve long-standing questions in Earth Sciences. Major factors limiting the application of this method are the very high analytical precision required for meaningful interpretations, the relatively complex sample preparation procedures, and the mass spectrometric corrections needed. In this paper we first briefly review the evolution of the analytical and standardization procedures and discuss the major remaining sources of uncertainty. We propose that the use of carbonate standards to project the results to the carbon dioxide equilibrium scale can improve interlaboratory data comparability and help to solve long-standing discrepancies between laboratories and temperature calibrations. The use of carbonates reduces uncertainties related to gas preparation and cleaning procedures and ensures equal treatment of samples and standards. We present a set of carbonate standards of diverse composition, discuss how they can be used to correct for mass spectrometric biases, and demonstrate that their use significantly improves the comparability among four laboratories. We propose that the use of these standards or of a similar set of carbonate standards will improve the comparability of data across laboratories.

DNA-encoded chemical libraries for the discovery of MMP-3 inhibitors.

Encoded self-assembling chemical (ESAC) libraries are characterized by the covalent display of chemical moieties at the extremity of self-assembling oligonucleotides carrying a unique DNA sequence for the identification of the corresponding chemical moiety. We have used ESAC library technology in a two-step selection procedure for the identification of novel inhibitors of stromelysin-1 (MMP-3), a matrix metalloproteinase involved in both physiological and pathological tissue remodeling processes, yielding novel inhibitors with micromolar potency.