Potential for identifying plant-based toxins on San hunter-gatherer arrowheads

The antiquity of the use of hunting poisons has received much attention in recent years. In this paper we present the results of a pilot study designed to detect the presence of organic compounds, typically of less than 1200 Da, from poisonous plants that may have been used as hunting poisons in the past. We used ultra-performance liquid chromatography connected to a Synapt G2 high-resolution MS-QTOF mass spectrometer (UPLC-QTOF-MS) to provisionally identify plant-based toxins present in (1) extracts of fresh plant material, (2) a blind control recipe consisting of three plant ingredients and (3) a Hei||om arrow poison of unknown ingredients. Although not all expected toxic compounds were identified, those that were identified compared favourably with those reported in the literature and confirmed through databases, specifically the Dictionary of Natural Products and ChemSpider. MS/MS fragmentation patterns and accurate mass were used for tentative identification of compounds because archaeological residues usually contain insufficient material for unambiguous identification using nuclear magnetic resonance. We highlight the potential of this method for accurately identifying plant-based toxins present on archaeological artefacts and unique (albeit non-toxic) chemical markers that may allow one to infer the presence of toxic plant ingredients in arrow poisons. Any chemical study of archaeological material should consider the unique environmental degradative factors and be sensitive to the oxidative by-products of toxic compounds

An integrated targeted and untargeted approach for the analysis of ergot alkaloids in cereals using UHPLC - hybrid quadrupole time-of-flight mass spectrometry

An ultra-high performance liquid chromatography hybrid quadrupole time of flight (Q-TOF) mass spectrometry (MS) method is described for the simultaneous quantitative determination of common ergot alkaloids and the screening, detection and identification of unexpected (less studied or novel) members of this class of toxic fungal secondary metabolites. The employed analytical strategy involves an untargeted data acquisition (consisting of full scan TOF MS survey and information dependent acquisition MS/MS scans) and the processing of data using both targeted and untargeted approaches. Method performance characteristics for the quantitative analysis of 6 common ergot alkaloids i.e. ergometrine, ergosine, ergotamine, ergocornine, ergocristine, ergokryptine and their corresponding epimers in rye were comparable to those previously reported for triple-quadrupole (QqQ) MS/MS. The method limits of quantification (LOQ) were in the range from 3 to 19 mu g/kg, and good linearity was observed for the different ergot alkaloids in the range from LOQ to 1000 mu g/kg. Furthermore, the method demonstrated good precision (relative standard deviations at 50 mu g/kg not higher than 14.6 and 16.2% for the intra-day and inter-day precision, respectively), and the trueness values at different concentration levels were all between 89 and 115%. The method was applied for the analysis of a set of 17 rye samples and demonstrated the presence of these ergot alkaloids in the range from <LOQ to 2,811 mu g/kg. Further mining of the same data based on a 'non-targeted peak finding' algorithm and the use of full MS and MS/MS accurate mass data allowed the detection and identification of 19 ergot alkaloids that are commonly not included in most analytical methods using QqQ instruments. Some of these alkaloids are reported for the first time in naturally contaminated samples

Organics in comet 67P – a first comparative analysis of mass spectra from ROSINA–DFMS, COSAC and Ptolemy

The ESA Rosetta spacecraft followed comet 67P at a close distance for more than 2 yr. In addition, it deployed the lander Philae on to the surface of the comet. The (surface) composition of the comet is of great interest to understand the origin and evolution of comets. By combining measurements made on the comet itself and in the coma, we probe the nature of this surface material and compare it to remote sensing observations. We compare data from the double focusing mass spectrometer (DFMS) of the ROSINA experiment on ESA's Rosetta mission and previously published data from the two mass spectrometers COSAC (COmetary Sampling And Composition) and Ptolemy on the lander. The mass spectra of all three instruments show very similar patterns of mainly CHO-bearing molecules that sublimate at temperatures of 275 K. The DFMS data also show a great variety of CH-, CHN-, CHS-, CHO2- and CHNO-bearing saturated and unsaturated species. Methyl isocyanate, propanal and glycol aldehyde suggested by the earlier analysis of the measured COSAC spectrum could not be confirmed. The presence of polyoxymethylene in the Ptolemy spectrum was found to be unlikely. However, the signature of the aromatic compound toluene was identified in DFMS and Ptolemy data. Comparison with remote sensing instruments confirms the complex nature of the organics on the surface of 67P, which is much more diverse than anticipated

Fixing Food Safety: Protecting America's Food Supply From Farm-to-Fork

Provides an overview of the major concerns regarding U.S. food safety, including an ineffective regulatory system, and of food-borne disease threats. Includes lists of recent outbreaks, major causes of food-borne illnesses, and recommended solutions

A case report of accidental intoxication following ingestion of foxglove confused with borage : high digoxinemia without major complications

Foxglove (Digitalis purpurea L.) leaves are frequently confused with borage (Borago officinalis L.), which is traditionally used as a food ingredient. Due to the presence of the cardiac glycosides, mostly digitoxin, foxglove leaves are poisonous to human and may be fatal if ingested. A 55-year-old Caucasian woman complaining weakness, fatigue, nausea, and vomiting was admitted to the Emergency Department. Her symptoms started following consumption of a home-made savory pie with 5 leaves from a plant bought in a garden nursery as borage. Digoxinemia was high (10.4\u2009\u3bcg/L). The patient was admitted to the cardiac intensive care unit for electrocardiographic monitoring. Two days after admission, a single episode of advanced atrioventricular (AV) block was recorded by telemetry, followed by a second-degree AV block episode. Plasma samples at day 11 were analysed by LC-MS spectrometry, and gitoxin was identified suggesting that this compound may be responsible for the clinical toxicity rather than digoxin. In the case of Digitalis spp. poisoning, laboratory data should be interpreted according to the clinical picture and method of analysis used since a variety of glycosides, which are chemically similar to the cardioactive glycosides but without or with fewer cardiac effects, may be incorrectly recognized as digoxin by the test, giving misleading results

A Simple Approach to Preventing the Next Housing Crisis-Why We Need ONe, What One Would Look Like, and Why Dodd-Frank Isn\u27t It

This article considers the adequacy of The Dodd-Frank Act in terms of its potential ability to prevent another crisis in the housing market. The author argues that Dodd-Frank, even if implemented broadly, will not address the key problem of excess complexity in the housing and financial markets. The author then suggests additional reform focusing on simplicity, exemplified by the existing regulatory framework in Denmark. Lastly, the author addresses the current political economy, which is blamed for making the passage of effective regulation too difficult

The Role of Scientific Discovery in the Establishment of the First Biological Weapons Programmes

YesThis report addresses the scientific and technological discoveries in the biological sciences that enabled the early interest in biological warfare to move from hurling infected corpses into enemy cities in ancient times, through use of small cultures of animal pathogens to sabotage enemy livestock in World War I, to the origins of organised military biological weapons (BW) programmes directed at humans, animals, and plants in the inter-war period. It builds on Dando¿s 1999 paper: The Impact of the Development of Modern Biology and Medicine on the Evolution of Offensive Biological Warfare Programs in the Twentieth Century.1 For the historical aspects of biological warfare programmes this report primarily draws from the Stockholm International Peace Research Institute volume: Biological and Toxin Weapons: Research, Development and Use from the Middle Ages to 1945.

Use of wood anatomy to identify poisonous plants: Charcoal of Spirostachys africana.

Spirostachys africana Sond. (tamboti/tambotie) is a woodland tree that is often found near water. It has a poisonous and purgative latex. The archaeological site of Sibudu, a rock shelter in KwaZulu-Natal, has evidence, from well-preserved charcoal and seeds, of past environments and wood use from approximately 77-38 thousand years ago (ka). As their uses and environmental indicators are different, it is critical to confidently distinguish among the three anatomically similar woods of the Euphorbiaceae: Spirostachys africana, Sclerocroton integerrimus and Shirakiopsis elliptica. A detailed anatomical study of reference and archaeological charcoal shows that xylem vessel width increases proportionally as vessel frequency decreases, from Spirostachys africana, Sclerocroton integerrimus to Shirakiopsis elliptica. Crystals of calcium oxalate are present in ray cells of Spirostachys africana, whereas silica bodies are present in ray cells of Sclerocroton integerrimus and Shirakiopsis elliptica. Using these features, the presence of Spirostachys africana was confirmed amongst hearth charcoal of the Spotty Camel layer, with an age of approximately 58 ka and of the Mottled Deposit occupational layer, with an age of approximately 49 ka. The presence of this charcoal, collected from ancient fireplaces or sieved from surrounding sediments, implies that people at Sibudu understood and used this poisonous tree to their advantage. We are encouraged in this view by the presence of many Cryptocarya woodii leaves found on the surface of 77-ka sedge bedding at Sibudu (Wadley L et al., Science. 2011;334:1388-1391). Cryptocarya woodii has insecticidal and larvacidal properties and members of the Laurel family are well known for their medicinal properties.NCS201