Gas chromatographic mass spectrometric detection of dihydroxy fatty acids preserved in the 'bound' phase of organic residues of archaeological pottery vessels.

A methodology is presented for the determination of dihydroxy fatty acids preserved in the ‘bound’ phase of organic residues preserved in archaeological potsherds. The method comprises saponification, esterification, silica gel column chromatographic fractionation, and analysis by gas chromatography/mass spectrometry. The electron ionisation mass spectra of the trimethylsilyl ether methyl ester derivatives are characterised by fragment ions arising from cleavage of the bond between the two vicinal trimethylsiloxy groups. Other significant fragment ions are [M–15]+., [M–31]+., m/z 147 and ions characteristic of vicinal disubstituted (trimethylsiloxy) TMSO? groups (?7,8, ?9,10,?11,12 and ?13,14: m/z 304, 332, 360 and 388, respectively). The dihydroxy fatty acids identified in archaeological extracts exhibited carbon numbers ranging from C16 to C22 and concentrations varying from 0.05 to 14.05 ?g g?1. The wide range of dihydroxy fatty acids observed indicates that this approach may be applied confidently in screening archaeological potsherds for the degradation products of monounsaturated fatty acids derived from commodities processed in archaeological pottery vessels

Immediate replacement of fishing with dairying by the earliest farmers of the NE Atlantic archipelagos

The appearance of farming, from its inception in the Near East around 12 000 years ago, finally reached the northwestern extremes of Europe by the fourth millennium BC or shortly thereafter. Various models have been invoked to explain the Neolithization of northern Europe; however, resolving these different scenarios has proved problematic due to poor faunal preservation and the lack of specificity achievable for commonly applied proxies. Here, we present new multi-proxy evidence, which qualitatively and quantitatively maps subsistence change in the northeast Atlantic archipelagos from the Late Mesolithic into the Neolithic and beyond. A model involving significant retention of hunter–gatherer–fisher influences was tested against one of the dominant adoptions of farming using a novel suite of lipid biomarkers, including dihydroxy fatty acids, ω-(o-alkylphenyl)alkanoic acids and stable carbon isotope signatures of individual fatty acids preserved in cooking vessels. These new findings, together with archaeozoological and human skeletal collagen bulk stable carbon isotope proxies, unequivocally confirm rejection of marine resources by early farmers coinciding with the adoption of intensive dairy farming. This pattern of Neolithization contrasts markedly to that occurring contemporaneously in the Baltic, suggesting that geographically distinct ecological and cultural influences dictated the evolution of subsistence practices at this critical phase of European prehistory

Engineering soil organic matter quality: Biodiesel Co-Product (BCP) stimulates exudation of nitrogenous microbial biopolymers

Biodiesel Co-Product (BCP) is a complex organic material formed during the transesterification of lipids. We investigated the effect of BCP on the extracellular microbial matrix or ‘extracellular polymeric substance’ (EPS) in soil which is suspected to be a highly influential fraction of soil organic matter (SOM). It was hypothesised that more N would be transferred to EPS in soil given BCP compared to soil given glycerol. An arable soil was amended with BCP produced from either 1) waste vegetable oils or 2) pure oilseed rape oil, and compared with soil amended with 99% pure glycerol; all were provided with 15N labelled KNO3. We compared transfer of microbially assimilated 15N into the extracellular amino acid pool, and measured concomitant production of exopolysaccharide. Following incubation, the 15N enrichment of total hydrolysable amino acids (THAAs) indicated that intracellular anabolic products had incorporated the labelled N primarily as glutamine and glutamate. A greater proportion of the amino acids in EPS were found to contain 15N than those in the THAA pool, indicating that the increase in EPS was comprised of bioproducts synthesised de novo. Moreover, BCP had increased the EPS production efficiency of the soil microbial community (μg EPS per unit ATP) up to approximately double that of glycerol, and caused transfer of 21% more 15N from soil solution into EPS-amino acids. Given the suspected value of EPS in agricultural soils, the use of BCP to stimulate exudation is an interesting tool to consider in the theme of delivering sustainable intensification

Measuring the soil-microbial interface: extraction of extracellular polymeric substances (EPS) from soil biofilms

Many soil microbes exist in biofilms. These biofilms are typified by variable quantities of extracellular polymeric substances (EPS: predominantly polysaccharides, glycoconjugates, and proteins) and the embedded microbial cells. A method to measure soil-EPS (the biofilm exclusive of microbial cells) has not yet been described. The present work investigates the potential of five extraction methods to estimate changes in soil-EPS content. A rationale for selection of appropriate EPS extraction and methodology is discussed, including the crucial consideration of both intracellular and extracellular contamination. EPS was developed in situ by provision of labile C (glycerol) to the microbial biomass of a moist soil and then applying desiccation stress. Only two out of the five extraction methods showed statistically significant increases in polysaccharide production responding to substrate addition. Humified organic matter, estimated by its humic acid equivalent (HAE) was used to indicate the degree of extracellular contamination, and/or creation of humic artefacts – both of which affect detection of changes in EPS. The HAE concentration was very high when applying original and modified methods designed to extract glomalin related soil protein (GRSP). Extraction methods involving heating with dilute sulphuric acid appeared to overestimate EPS-polysaccharide. Using microbial ATP as an indicator of cell-lysis, confidence could only be ascribed to EPS extraction with cation exchange resin. Using this method, the expected increases in EPS-polysaccharide were clearly apparent. The HAE/protein ratios of EPS extracts were also lowest with cation exchange – indicating this method did not cause excessive contamination from humified soil organic matter or create related artefacts

Supersonic Downflows at the Umbra-Penumbra Boundary of Sunspots

High resolution spectropolarimetric observations of 3 sunspots taken with Hinode demonstrate the existence of supersonic downflows at or close to the umbra-penumbra boundary which have not been reported before. These downflows are confined to large patches, usually encompassing bright penumbral filaments, and have lifetimes of more than 14 hr. The presence of strong downflows in the center-side penumbra near the umbra rules out an association with the Evershed flow. Chromospheric filtergrams acquired close to the time of the spectropolarimetric measurements show large, strong, and long-lived brightenings in the neighborhood of the downflows. The photospheric intensity also exhibit persistent brightenings comparable to the quiet Sun. Interestingly, the orientation of the penumbral filaments at the site of the downflows is similar to that resulting from the reconnection process described by Ryutova et al. The existence of such downflows in the inner penumbra represents a challenge for numerical models of sunspots because they have to explain them in terms of physical processes likely affecting the chromosphere.Comment: Accepted for publication in Ap

Runoff- and erosion-driven transport of cattle slurry:linking molecular tracers to hydrological processes

The addition of cattle slurry to agricultural land is a widespread practise, but if not correctly managed it can pose a contamination risk to aquatic ecosystems. The transport of inorganic and organic components of cattle slurry to watercourses is a major concern, yet little is known about the physical transport mechanisms and associated fluxes and timings of contamination threats. Therefore, the aim of the study was to ascertain the importance of flow pathway partitioning in the transport (fluxes and timing) of dissolved and particulate slurry-derived compounds with implications for off-site contamination. A series of rainfall–runoff and erosion experiments were carried out using the TRACE (Test Rig for Advancing Connectivity Experiments) experimental hillslope facility. The experiments allowed the quantification of the impact of changing slope gradient and rainfall intensity on nutrient transport from cattle slurry applied to the hillslope, via surface, subsurface, and vertical percolated flow pathways, as well as particulate transport from erosion. The dissolved components were traced using a combination of ammonium (NH₄⁺) and fluorescence analysis, while the particulate fraction was traced using organic biomarkers, 5<i>β</i>-stanols. Results showed that rainfall events which produced flashy hydrological responses, resulting in large quantities of surface runoff, were likely to move sediment and also flush dissolved components of slurry-derived material from the slope, increasing the contamination risk. Rainfall events which produced slower hydrological responses were dominated by vertical percolated flows removing less sediment-associated material, but produced leachate which could contaminate deeper soil layers, and potentially groundwater, over a more prolonged period. Overall, this research provides new insights into the partitioning of slurry-derived material when applied to an unvegetated slope and the transport mechanisms by which contamination risks are created

Holocene lake sediment core sequences from Lochnagar, Cairngorm Mts., Scotland - UK final report for CHILL-10,000

The CHILL 10,000 research objective at Lochnagar is to examine proxy data for temperature and climate conditions. Changes in lake sediment stratigraphical data can be used to reconstruct past conditions. These proxies include organic and minerogenic matter as a bulk proxy for catchment and within-lake productivity, chironomids as a proxy for air temperature, diatoms as an indicator for lake water pH, pollen as an indicator of catchment vegetation and finally biomarkers to help determine changes in proportions of organic source material within the lake mud

The effect of trophic level on individual amino acid δ15N values in a terrestrial ruminant food web

Bulk collagen δ15N analysis is widely used to investigate past diet and trophic positions, but these values average the δ15N values of the constituent amino acids. Compound–specific isotope analysis of amino acids (AAs) can help elucidate the complex metabolic effects underpinning bulk δ15N values. Although trophic level effects on individual AA δ15N values have been investigated in aquatic and terrestrial invertebrate food webs, most archaeological applications involve terrestrial herbivores, hence a greater understanding of these effects between diet and consumer in this food chain is required. The North Wyke Farm Platform provided baseline nitrogen isotope information for cattle grazing on a Lolium perenne- dominated pasture. Bulk dentine δ15N values show a shift expected for a one trophic level increase, but obscure insight into the underlying metabolic processes that cause this change in value. However, determination of AA δ15N values of hydrolysable plant protein and cattle tooth dentine clarifies the trophic effect on consumer AA δ15N values. The observed trophic shift in the studied system is different from previously studied food webs, with a trophic enrichment factor, based on the δ15N values of glutamate and phenylalanine, of 4.0‰ compared to 7.6‰ commonly used in ecological and archaeological studies. This emphasises the need to understand the trophic shifts in the particular food web being investigated in order to apply isotopic investigations in archaeological contexts

Interpreting ancient food practices:Stable isotope and molecular analyses of visible and absorbed residues from a year-long cooking experiment

Chemical analyses of carbonized and absorbed organic residues from archaeological ceramic cooking vessels can provide a unique window into the culinary cultures of ancient people, resource use, and environmental effects by identifying ingredients used in ancient meals. However, it remains uncertain whether recovered organic residues represent only the final foodstuffs prepared or are the accumulation of various cooking events within the same vessel. To assess this, we cooked seven mixtures of C3 and C4 foodstuffs in unglazed pots once per week for one year, then changed recipes between pots for the final cooking events. We conducted bulk stable-isotope analysis and lipid residue analysis on the charred food macro-remains, carbonized thin layer organic patina residues and absorbed lipids over the course of the experiment. Our results indicate that: (1) the composition of charred macro-remains represent the final foodstuffs cooked within vessels, (2) thin-layer patina residues represent a mixture of previous cooking events with bias towards the final product(s) cooked in the pot, and (3) absorbed lipid residues are developed over a number of cooking events and are replaced slowly over time, with little evidence of the final recipe ingredients

Flow Field Evolution of a Decaying Sunspot

We study the evolution of the flows and horizontal proper motions in and around a decaying follower sunspot based on time sequences of two-dimensional spectroscopic observations in the visible and white light imaging data obtained over six days from June~7 to~12, 2005. During this time period the sunspot decayed gradually to a pore. The spectroscopic observations were obtained with the Fabry-P\'{e}rot based Visible-Light Imaging Magnetograph (VIM) in conjunction with the high-order adaptive optics (AO) system operated at the 65 cm vacuum reflector of the Big Bear Solar Observatory (BBSO). We apply local correlation tracking (LCT) to the speckle reconstructed time sequences of white-light images around 600 nm to infer horizontal proper motions while the Doppler shifts of the scanned \FeI line at 630.15 nm are used to calculate line-of-sight (LOS) velocities with sub-arcsecond resolution. We find that the dividing line between radial inward and outward proper motions in the inner and outer penumbra, respectively, survives the decay phase. In particular the moat flow is still detectable after the penumbra disappeared. Based on our observations three major processes removed flux from the sunspot: (a) fragmentation of the umbra, (b) flux cancelation of moving magnetic features (MMFs; of the same polarity as the sunspot) that encounter the leading opposite polarity network and plages areas, and (c) flux transport by MMFs (of the same polarity as the sunspot) to the surrounding network and plage regions that have the same polarity as the sunspot.Comment: 9 pages, 7 figures, The Astrophysical Journal, accepted September, 200