Predicting protein decomposition: the case of aspartic-acid racemization kinetics

The increase in proportion of the non-biological (D-) isomer of aspartic acid (Asp) relative to the L- isomer has been widely used in archaeology and geochemistry as a tool for dating. The method has proved controversial, particularly when used for bones. The non-linear kinetics of Asp racemization have prompted a number of suggestions as to the underlying mechanism(s) and have led to the use of mathe- matical transformations which linearize the increase in D-Asp with respect to time. Using one example, a suggestion that the initial rapid phase of Asp racemization is due to a contribution from asparagine (Asn), we demonstrate how a simple model of the degradation and racemization of Asn can be used to predict the observed kinetics. A more complex model of peptide bound Asx (Asn+Asp) racemization, which occurs via the formation of a cyclic succinimide (Asu), can be used to correctly predict Asx racemi- zation kinetics in proteins at high temperatures (95-140 °C). The model fails to predict racemization kinetics in dentine collagen at 37 °C. The reason for this is that Asu formation is highly conformation dependent and is predicted to occur extremely slowly in triple helical collagen. As conformation strongly in£uences the rate of Asu formation and hence Asx racemization, the use of extrapolation from high temperatures to estimate racemization kinetics of Asx in proteins below their denaturation temperature is called into question. In the case of archaeological bone, we argue that the D:L ratio of Asx re£ects the proportion of non- helical to helical collagen, overlain by the e¡ects of leaching of more soluble (and conformationally unconstrained) peptides. Thus, racemization kinetics in bone are potentially unpredictable, and the proposed use of Asx racemization to estimate the extent of DNA depurination in archaeological bones is challenged

A geochronological review of magmatism along the external margin of Columbia and in the Grenville-age orogens forming the core of Rodinia

A total of 4344 magmatic U-Pb ages in the range 2300 to 800 Ma have been compiled from the Great Proterozoic Accretionary Orogen along the margin of the Columbia / Nuna supercontinent and from the subsequent Grenvillian collisional orogens forming the core of Rodinia. The age data are derived from Laurentia (North America and Greenland, n = 1212), Baltica (NE Europe, n = 1922), Amazonia (central South America, n = 625), Kalahari (southern Africa and Dronning Maud Land in East Antarctica, n = 386), and western Australia (n = 199). Laurentia, Baltica, and Amazonia (and possibly other cratons) most likely formed a ca. 10 000-km-long external active continental margin of Columbia from its assembly at ca. 1800 Ma until its dispersal at ca. 1260 Ma, after which all cratons studied were involved in the Rodinia-forming Grenvillian orogeny. However, the magmatic record is not smooth and even but highly irregular, with marked peaks and troughs, both for individual cratons and the combined data set. Magmatic peaks typically range in duration from a few tens of million years up to around hundred million years, with intervening troughs of comparable length. Some magmatic peaks are observed on multiple cratons, either by coincidence or because of paleogeographic proximity and common tectonic setting, while others are not. The best overall correlation, 0.617, is observed between Baltica and Amazonia, consistent with (but not definitive proof of) their being close neighbours in a SAMBA-like configuration at least in Columbia, and perhaps having shared the same peri-Columbian subduction system for a considerable time. Correlation factors between Laurentia and Baltica, or Laurentia and Amazonia, are below 0.14. Comparison between the Grenville Province in northeastern Laurentia and the Sveconorwegian Province in southwestern Fennoscandia (Baltica) shows some striking similarities, especially in the Mesoproterozoic, but also exhibits differences in the timing of events, especially during the final Grenville-Sveconorwegian collision, when the Sveconorwegian evolution seems to lag behind by some tens of million years. Between the other cratons, the evolution before and during the final Grenvillian collision is also largely diachronous. After 900 Ma, magmatic activity had ceased in all areas investigated, attesting to the position of most of them within the stable interior of Rodinia.publishedVersio

A counterfactual approach to measure the impact of wet grassland conservation on UK breeding bird populations

Wet grassland wader populations in the United Kingdom have experienced severe declines over the last three decades. To help mitigate these declines, the Royal Society for the Protection of Birds (RSPB) has restored and managed lowland wet grassland nature reserves to benefit these and other species. However, the impact that these reserves have on bird population trends has not been experimentally evaluated, as appropriate control populations do not readily exist. In this study, we compare population trends from 1994 ‐ 2018 for five bird species of conservation concern that breed on these nature reserves with counterfactual trends using matched breeding bird survey observations. Our results showed positive effects of conservation interventions for all four wader species that these reserves aim to benefit: Lapwing (Vanellus vanellus), Redshank (Tringa totanus), Curlew (Numenius arquata) and Snipe (Gallinago gallinago). There was no positive effect of conservation interventions on reserves for the passerine, Yellow Wagtail (Motacilla flava). We compared reserve trends with three different counterfactuals, based on different scenarios of how reserve populations could have developed in the absence of conservation, and found that reserve trends performed better regardless of the counterfactual used. Our approach using monitoring data to produce valid counterfactual controls is a broadly applicable method allowing large‐scale evaluation of conservation impact

Lipids as carriers of anthropogenic signals from prehistory

Studies performed during the last two decades have shown that lipids are preserved in association with a wide range of artefacts and ecofacts recovered from archaeological sites, e.g. pottery vessels and skeletal remains. The majority of work in this area has focused on the use of molecular structures ('biomarkers') and distributions ('fingerprints') to assess the nature and origin of commodities associated with past cultural, economic and agricultural practices. However, since lipids, like all other classes of biomolecule, are affected by degradation (both pre- and post-burial), emphasis is now being placed on the complementary use of diagenetically robust, compound-specific stable isotope measurements to enhance the scope and reliability of archaeological interpretations. A feature of the δ(13)C values of individual lipids, rather than bulk measurements of biochemically more heterogeneous materials, lies in their capacity to reflect differences in both the isotopic composition of the carbon sources used in their biosynthesis and the routing of dietary lipids and their metabolites in consumer organisms. This isotopic information, accessible by gas chromatography-combustion-isotope ratio mass spectrometry, has opened up new avenues of investigation concerning human activity in prehistory