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• W2180357022 abstract "Direct analysis in real time (DART) mass spectrometry has potential for rapid characterization of residues in and on archaeological materials, often without the need for extraction and sample preparation. These residues may provide insight into people’s behavior in the ancient past, including what they ate and drank and what plants they used. Residues change over time through oxidation, loss of water-soluble components during washing, and contamination from burial and handling. We are investigating how nicotine residues in historic smoking pipes from Historic St. Mary’s City, Maryland, have changed through time. To understand how residues change as they age and decompose, we are studying tobacco pipes that have been excavated and not cleaned, as well as pipes that have been cleaned and processed by the Historic St. Mary City museum. Nicotine and several of its oxidation products are readily observed in replica residues analyzed with DART-MS, even after the ceramic surfaces have been cleaned. INTRODUCTION Archaeology is the study of the human past through the artifacts left behind. Usually, these artifacts are hard, durable materials like ceramics and stone tools. In the past 20 or so years, researchers have been interested in the residues adhering to those durable artifacts and how the molecules that make up those residues can inform us about past human behavior. Chemical analysis of residues provides information about what foods people included in their diets, how they processed those foods, and even what medicines and dyes they might have used. 2 1 Torres: Dart-Ms Analysis of Historic Tobacco Pipes Published by DigitalCommons@EMU, 118 While archaeological materials are evidence from the past, forensic evidence tells the story of a modern-day crime. One technique that has revolutionized both archaeological and forensic sciences is DNA amplification using the polymerase chain reaction (PCR). PCR has fundamentally changed the way in which forensic evidence is treated. In archaeological sciences, PCR has been used to amplify DNA in a number of different materials, including rock paintings, with questionable success. DNA analysis was also undertaken to study artifacts from the Boston Saloon in Virginia City, Nevada. Remarkably, the user of a clay tobacco pipe stem found at the site was shown to have been female, leading to significant questions about the population of that site. Many analytical methods can be applied to identifying archaeological residues, most of which include some kind of separation step. Separation is best done with chromatography, in the gas or liquid phase, and often in conjunction with mass spectrometry in order to identify the separated molecules. Gas chromatography-mass spectroscopy (GC-MS) and liquid chromatography-mass spectroscopy (LC-MS) are the most widely applied in archaeological residues. This report focuses on methods used for identification of nicotine or tobacco residues in archaeological samples. Both GC-MS and LC-MS were successfully used to investigate Mayan vessels from the Late Classical period for traces of nicotine. Rafferty has published several reports on the analysis of smoking pipe residues, primarily using GC-MS with positive results. Tushingham also used GC-MS, with a rigorous approach to investigate tobacco pipe residues. While GC-MS has been shown to be a reliable method for identifying nicotine and its derivatives on archaeological materials, it requires the samples to be extracted and often derivatized, which is both time-consuming and often destructive to the artifacts. Rafferty et al. unsuccessfully attempted to use Raman microscopy to nondestructively study pipe residues, due to Raman’s lack of sensitivity and interferences from other substances. Nondestructive or even noninvasive methods for identifying residues are generally preferred, but few have as yet been proven effective. Sylvia A. Torres 2 McNair Scholars Research Journal, Vol. 7 [], Iss. 1, Art. 11 http://commons.emich.edu/mcnair/vol7/iss1/11 119 Direct analysis in real time (DART) ionization for mass spectrometric analysis was first reported in 2005 and was developed in 2005 as a means of identifying small molecules on surfaces without sample preparation. DART can be used to determine the chemical composition of a sample that is directly introduced to the ion source in less than a minute. DART-MS has been widely adopted in forensic science laboratories because of its ability to produce instantaneous results. In a recent study, DARTMS was used in a sexual assault case to identify non-DNA trace evidence (e.g. lubricant residue, trace fibers). DART-MS has great potential in applications related to archaeological and other cultural heritage materials. Selvius DeRoo and Armitage reported using DART with high resolution time-offlight to identify organic dye compounds in cotton textiles without sample preparation. Further work from that group on dyed cotton fibers from a late 19 century treatise showed that DART-MS could be used to identify several different organic colorants. Dyes in historic wool textiles from European tapestries were also readily identified using DART-MS. Of relevance to this project, DART-MS was also used in the identifying food biomarkers on archaeological ceramics that had been exposed to burial and then cleaned. All analytical methods, particularly those used in forensic science, must produce results that are reliable, consistent, and without systematic errors or bias. Validation is the way that analytical chemists prove a method works as intended and provides results with known accuracy, precision and limits of detection. In the case of identifying archaeological residues on ceramics, the selected analytical technique must be able to identify the molecules of interest on ceramics that are old, contaminated by burial, and often cleaned upon excavation. While it is difficult at best to obtain standard ancient materials that have aged or been processed in known ways, it is possible to make mock-up samples that simulate ancient materials and can then be used to validate a method. With validation, an analytical method lends credibility to the measurements and eliminates the need for repeated analyses with new, untried methodologies. Tushingham’s work made progress on validating the GC-MS analysis of tobacco residues in archaeological samples. DART-MS Analysis of Historic Tobacco Pipes to Investigate the Preservation of Nicotine Residues 3 Torres: Dart-Ms Analysis of Historic Tobacco Pipes Published by DigitalCommons@EMU, 120 The intent of this study was to use DART-MS to identify nicotine in 17-century ceramic smoking pipes excavated from St. Mary’s City, Maryland. The samples selected for study were all old and had likely undergone oxidation, had been handled and contaminated in the museum, and had been cleaned with water, possibly removing any water soluble components. The method was validated using mock-up samples of tobacco residue on ceramics that were prepared in the laboratory and subjected to similar conditions. This work will help establish the credibility of using DART-MS for identifying archaeological residues. MATERIALS AND METHODS" @default.
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• W2180357022 date "2011-05-25" @default.
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• W2180357022 title "Drive for Muscularity and Drive for Thinness: The Impact of Pro-Anorexia Websites" @default.
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