Chemical Residue Analysis Research Articles

Assessment of genetic effects and pesticide exposure of farmers in NW Greece

The present study aims at evaluating potential genotoxic and cytotoxic effects caused by the occupational exposure of farmers to pesticide mixtures in the Aitoloakarnania Prefecture (Greece). The aforementioned assessment was conducted through in vivo Cytokinesis Block Micronucleus assay (CBMN assay) in peripheral blood lymphocytes, in relation to chemical analysis of pesticide residues in blood samples. The exposure of the farmers' population studied to different combinations of pesticides induced significant differences in the frequencies of micronuclei (MN) compared to those of the control group. Furthermore, our results indicated a possible clastogenic and aneugenic effect of pesticides on the genetic material of the farmers exposed. Five pesticides (trifluralin, chlorpyriphos methyl, metolachlor, fenthion and dimethoate) and three metabolites (fenthion sulfone, fenthion sulfoxide and 4,4′ DDE) were detected in the 62.5% of blood samples, with mean concentrations ranging from 0.4 ng/ml to 48 ng/ml. Since the farmers studied probably exhibit detectable levels of systematic exposure to the pesticides applied, continuous educational programs focused on the rational and safe use of pesticides, together with implementation of risk communication strategies among farmers are highly recommended.

Flame-retardant polyurethane elastomer based on aluminum salt of monomethylphosphinate

The flame retardancy of polyurethane (PU) elastomer based on aluminum monomethylphosphinate (MeP-Al) was investigated. Thermal analysis, evolved gas analysis (TG-FTIR), flammability tests (LOI, UL 94), heat release rate (HRR) (microcombustion calorimeter), and chemical analysis of residues (SEM–EDX and FTIR) were used to investigate the flame-retardant performance and mechanism of the PU/MeP-Al. Results show that adding MeP-Al endows PU desired flame retardancy and anti-dripping property. The sample containing 20 mass% of MeP-Al passes the UL 94 V0 rating with LOI value of 29.6% and no dripping during combustion. Moreover, the heat release during combustion and the amount of organic volatile from PU decomposition are significantly reduced. The good flame retardancy, anti-dripping property, dramatically a reduction in release of heat and organic compounds are attributed to the efficient action of the MeP-Al in both the gas and condensed phase. In the gas phase, the MeP-Al decomposes into monomethylphosphinic acid to inhibit flame and reduces the heat release. In the condensed phase, MeP-Al turns into the tough aluminum pyrophosphonate and promotes PU to form stable carbonaceous char by interacting with PU.

Detection of Gasoline Residues Present in Household Materials Via Headspace-solid Phase Microextraction and Gas Chromatography‒mass Spectrometry

This paper describes the detection and persistence of gasoline residues present in household materials, cotton fabric, cardboard, and carpet. These samples were spiked with 50 μL of gasoline and dried for a controlled period of time at room temperature prior to chemical analysis. The extraction and chemical analysis of gasoline residues were conducted via headspace-solid phase microextraction and gas chromatography‒mass spectrometry, respectively. Our data showed that gasoline residues were detected in the cotton fabric samples after up to 7 days of drying, while both the cardboard and carpet samples could retain gasoline residues for longer than 3 weeks. The adoption of small-sized vials for headspace analysis improved the detection limit of gasoline residues in the samples. The physical features of the samples, such as porosity, thickness, and number of layers, were found to be more important than chemical compositions for the increased persistence of gasoline residues.

Novel LIBS method for micro‐spatial chemical analysis of inorganic gunshot residues

AbstractThis study developed a reliable laser‐induced breakdown spectroscopy (LIBS) screening approach capable of detecting GSR in just a few minutes with minimal damage to the sample, high specificity, and sensitivity. Moreover, a novel micro‐sampling method was developed to gather three‐dimensional data of the simultaneous occurrence of IGSR markers from a discrete space. The method is capable of micro‐spatial chemical analysis from just two laser shots fired at an area of 100‐μm diameter. The performance of the micro‐spot method is compared with our previously published bulk‐line method. Superior accuracy, spatial information of IGSR distribution in the sample, and a less invasive sampling are some of the advantages of the newly proposed method. A benefit afforded by this approach is the use of the universal hand's collection method currently used by practitioners, while leaving over 99% of the stub left unaltered for further analysis.Machine learning algorithms were used for the classification of samples derived from shooters' hands versus nonshooters hands, based on their LIBS spectrochemical data. Four different approaches—critical threshold, logistic regression, naïve Bayes, and neural networks—were applied to examine the performance and accuracy of two different ablation patterns (micro‐spot and bulk‐line mode). A validation set of 326 samples originated from 51 nonshooters and 56 known shooters resulted in an overall accuracy between 87% and 100%, depending on the ablation pattern and the type of prediction model applied. The incorporation of this rapid screening and statistical decision‐making approach could offer more efficient case management in firearm‐related investigations.

Birch-bark tar in the Roman world: the persistence of an ancient craft tradition?

Abstract

The promise and potential pitfalls of acid leaching for Pb[sbnd]Pb chronology

Acid leaching has been widely used in Pb–Pb chronology especially on meteorite samples, as it enhances the precision and accuracy of the chronology by separating radiogenic Pb from non-radiogenic Pb in the samples. Yet, the detailed mechanism of the radiogenic Pb separation remains elusive. Here we report scanning electron microscopy observations of acid-leached minerals from three achondrites that were previously analyzed for pyroxene PbPb dating (D'Orbigny, Ibitira and Northwest Africa 6704), and one stony‑iron meteorite (Brenham). Moreover, we present chemical analysis of acid leachates and residues of pyroxene and whole-rock fractions from the three achondrites using inductively coupled plasma mass spectrometry. The combined results reveal the resistance of minerals to acid treatments with HNO3, HCl, and HF and, in turn, allow us to explore the prospects and limitations of acid leaching for PbPb chronology. In particular, we show that (i) washing with dilute acids can efficiently liberate contaminant terrestrial Pb adsorbed on the mineral surface; (ii) hot and more concentrated (~6 M) HNO3 and HCl can separate pyroxenes from sulfides and anorthitic plagioclase that are highly enriched in initial non-radiogenic Pb; (iii) albitic plagioclase and pyroxenes show limited dissolution during the HNO3 and HCl treatments, but are progressively leached by hot 1 M HF, making it difficult to separate them from each other; and (iv) within single pyroxene grains having exsolved lamellar textures, high-Ca lamellae are more efficiently leached by the HF treatment than low-Ca ones. In the context of a two-stage Pb isotopic evolution model for pyroxene lamellae, we demonstrate that heterogeneous and incomplete dissolution of pyroxene lamellae with dilute HF can result in inaccurate PbPb age estimates. This may account for previously observed scattered Pb isotopic data for meteorite samples that were taken as evidence for isotope fractionation in a radiogenic Pb component during HF treatments.

Characterizing the Urban Mine—Challenges of Simplified Chemical Analysis of Anthropogenic Mineral Residues

Anthropogenic mineral residues are characterized by their material complexity and heterogeneity, which pose challenges to the chemical analysis of multiple elements. However, creating an urban mine knowledge database requires data using affordable and simple chemical analysis methods, providing accurate and valid results. In this study, we assess the applicability of simplified multi-element chemical analysis methods for two anthropogenic mineral waste matrices: (1) lithium-ion battery ash that was obtained from thermal pre-treatment and (2) rare earth elements (REE)-bearing iron-apatite ore from a Swedish tailing dam. For both samples, simplified methods comprising ‘in-house’ wet-chemical analysis and energy-dispersive X-ray fluorescence (ED-XRF) spectrometry were compared to the results of the developed matrix-specific validated methods. Simplified wet-chemical analyses showed significant differences when compared to the validated method, despite proven internal quality assurance, such as verification of sample homogeneity, precision, and accuracy. Matrix-specific problems, such as incomplete digestion and overlapping spectra due to similar spectral lines (ICP-OES) or element masses (ICP-MS), can result in quadruple overestimations or underestimation by half when compared to the reference value. ED-XRF analysis proved to be applicable as semi-quantitative analysis for elements with mass fractions higher than 1000 ppm and an atomic number between Z 12 and Z 50. For elements with low mass fractions, ED-XRF analysis performed poorly and showed deviations of up to 90 times the validated value. Concerning all the results, we conclude that the characterization of anthropogenic mineral residues is prone to matrix-specific interferences, which have to be addressed with additional quality assurance measures.

Community Identity and Shared Practice at Actuncan, Belize

Shared identities create deep historical ties to community spaces and can facilitate or constrict political expansion. This research examines the relationship between the ways in which families engaged local landscapes and developed shared identities at Actuncan, Belize, during the Terminal Classic period, a time when the city experienced population growth as surrounding centers declined. The nature and location of activity patterns in and around three residential groups allow inferences about shared practices and the expression of identities that those activities enabled and constrained. Importantly, this research includes investigations of both residential groups and architecturally free areas. It uses multiple methods to explore activities and to produce overlapping datasets, including excavation and analysis of macroartifacts, microartifacts, and soil chemical residues. The results suggest that Actuncan residents used not only the formal patio spaces of residential groups but also the interstitial spaces between them. Moreover, one residential group, Group 1, appears to have been a locus for distinct activities including sequential burials and, possibly, affiliative ritual practices connected to ancestral landscape use. Understanding relationships among residents is an important foundation for exploring broader political dynamics, including relationships between residents and rulers and how rulers created, legitimized, and maintained power and authority.

Investigations into sampling approaches for chemical analysis of latent fingermark residue

The quantitative variation in latent fingermark deposits sampled from the same donor (intra-donor) poses considerable challenges to studies into the chemical composition of latent fingermarks. The work presented here investigates approaches to the sampling of latent fingermark residues within this context. The amount of squalene in fingermarks deposited on non-porous surfaces, determined by GC–MS, was used as an indicator of the amount of non-polar material present. It was found that the percentage difference of squalene between deposits from two hands at a given time, without controlling the deposition force, was in the range of 4–100%. This was reduced to 0–44% in alternative sampling approaches where deposition force was controlled. These results demonstrate the significant influence of sampling on subsequent chemical analysis of fingermark residues, and offer possible sampling strategies to overcome issues associated with intra-donor variation.

RESIDUE ANALYSIS OF GRINDING STONES FROM CHALCOLITHIC GÜLPINAR

This study presents the preliminary results of residue analysis of grinding stones recovered from the Early Chalcolithic 2 and Middle Chalcolithic period settlements (Gülpınar II and Gülpınar III) in the Sanctuary of Apollo Smintheus (Smintheion), located in the southwestern corner of the modern Biga Peninsula (Ancient Troad) in north-western Anatolia. The Early Chalcolithic 2 period settlement at Gülpınar II has been dated to 5320-4940 BC, while the Middle Chalcolithic period settlement at Gülpınar III superimposing it has radiocarbon dates ranging between 4930 and 4450 BC. Excavations at Chalcolithic Gülpınar between 2004 and 2014 revealed a total of 453 ground stone tools. This work in this context residue analyze of total of 28 grinding stones that were uncovered from these two Early Chalcolithic 2 and Middle Chalcolithic cultural levels. Chemical analysis of residue on stone tools has become a common research technique used in archaeology science. Chemical residues in and on the working surface of used grinding tools lead us to consider the context of the tool usage. The widely-used Gas Chromatography–Mass Spectrometry (GC-MS) method was selected for analyses of the grinding stones from Chalcolithic Gülpınar. The chemical analysis and preliminary results obtained from Gülpınar samples are outlined in this study. Results show evidence of the distinctive lipid organic residues pentacosane and heptacosane as minor and trace constituents in some of the essential oils of edible crops and the major fatty acids of octadecanoic (stearic) and palmitic (oleic). Palmitic acid is also a major component of the oil found in dairy products and abundant in animal fat. These results may contribute to approaches that aim to explain how prehistoric societies carried out processing of organic and inorganic raw materials.

Detecting and discriminating pyrethroids with chemiresistor sensors

Environmental contextRegular insecticide treatments on the interior of aircraft impedes the spread of mosquitos and other pests internationally, but border protection agencies lack effective tools to ensure airlines have complied. We report the first use of chemiresistor sensors to detect and identify insecticide residue on an interior aircraft surface. The method could be developed into a tool that helps lower the risk of vector-borne diseases like malaria entering international ports. AbstractAustralia and other island nations are protected from stowaway pest vectors, like mosquitos, by aircraft disinsection – spraying the airplane interior with an insecticide. It is a simple biosecurity measure that can reduce the spread of malaria, Zika and other mosquito-borne diseases. However, checking airline compliance and the efficacy of the insecticide residue is a difficult task for border protection officials, which requires either a live fly bioassay or off-site laboratory testing. Neither of these methods are ideal for the hectic schedules of airlines. As such, we propose using gold nanoparticle chemiresistor sensor arrays, to detect and identify insecticide residue on the interior surface of aircraft. We have shown that hexanethiol functionalised sensors have a limit of detection of 3 parts per billion (ppb) for permethrin in solution and have a broad dynamic range responding to concentrations up to 1000 ppb. The chemical residues of three different insecticide products were lifted off an interior aircraft surface and identified with an array of seven uniquely functionalised sensors. This is the first ever demonstration of gold nanoparticle chemiresistor sensors being used for the analysis of chemical residues. These sensors have the potential to rapidly check the efficacy of insecticide residues on aircraft surfaces.

Biomolecular archaeology reveals ancient origins of indigenous tobacco smoking in North American Plateau

Chemical analysis of residues contained in the matrix of stone smoking pipes reveal a substantial direct biomolecular record of ancient tobacco (Nicotiana) smoking practices in the North American interior northwest (Plateau), in an area where tobacco was often portrayed as a Euro-American-introduced postcontact trade commodity. Nicotine, a stimulant alkaloid and biomarker for tobacco, was identified via ultra-performance liquid chromatography-mass spectrometry in 8 of 12 analyzed pipes and pipe fragments from five sites in the Columbia River Basin, southeastern Washington State. The specimens date from 1200 cal BP to historic times, confirming the deep time continuity of intoxicant use and indigenous smoking practices in northwestern North America. The results indicate that hunting and gathering communities in the region, including ancestral Nez Perce peoples, established a tobacco smoking complex of wild (indigenous) tobacco well before the main domesticated tobacco (Nicotiana tabacum) was introduced by contact-era fur traders and settlers after the 1790s. This is the longest continuous biomolecular record of ancient tobacco smoking from a single region anywhere in the world-initially during an era of pithouse development, through the late precontact equestrian era, and into the historic period. This contradicts some ethnohistorical data indicating that kinnikinnick, or bearberry (Arctostaphylos uva-ursi) was the primary precontact smoke plant in the study area. Early use likely involved the management and cultivation of indigenous tobaccos (Nicotiana quadrivalvis or Nicotiana attenuata), species that are today exceedingly rare in the region and seem to have been abandoned as smoke plants after the entry of trade tobacco.

"Earthworm Glutathione-Glutathione-S-Transferase: A Biomarker in Ecological Risk Assessment"

Modernization of human society generates numerous chemical from different sources and stimulate serious hazard to the ecosystem. Consequently, people are exposed to thousands of chemicals on daily basis by food, air, water, soil, dust, or the products we use without knowing their harmful effect. It’s not easy for people to identify if those chemicals are risky to their wellbeing or not. These encountered problems require immediate scientific attention to find appropriate and cost effective solutions. Most ecological risk assessments are based on chemical residue analysis of environmental parameters, such as surface water, sediments and soils in addition to determination of species diversity and density of wildlife, though the biological significance of measured chemical concentrations are not so specific and quantitative [1].

Integrated methodologies in the study of pottery function

The paper describes the application of integrated methodologies for the reconstruction of functional aspects of archaeological pottery, through spatial analysis of ceramic functional categories by GIS tools and chemical analysis of organic residues by gas chromatography-mass spectrometry (GC-MS). The research focused on the pottery assemblages from the archaic building (6 th century BC) identified in the Messapian settlement of Castello di Alceste (San Vito dei Normanni, Apulia, Italy). The application of integrated approaches contributed to better understand the role played by ceramics and their content in different functional areas.

Residue analysis, use-wear patterns, and replicative studies indicate that sandstone tools were used as reamers when producing shell fishhooks on San Nicolas Island, California

Elucidating the tools and production steps involved in manufacturing the characteristic circular shell fishhooks found on the California Channel Islands has been a long-standing problem in California archaeology. A prehistoric production site for shell fishhooks excavated on the most remote island, San Nicolas Island, has provided a rare opportunity to examine manufacturing sequences. We have previously employed a multidisciplinary research approach to demonstrate that fishhook production at this site involved using sandstone slabs as abraders, or “saws”. Here, we use chemical residue analysis, replicative experiments, and microwear patterns to show that fishhook production also involved the use of small pointed pieces of sandstone as reamers. These results bring us one step closer to understanding the complete prehistoric toolkit used for production of circular shell fishhooks.

Flame-retardant thermoplastic polyester based on multiarm aluminum phosphinate for improving anti-dripping

A novel multiarm aluminum salt of pentaerythrityl ester of tetra(carboxyethylmethylphosphinic acid) (Alcpp) was synthesized and added into thermoplastic polyester elastomer (TPEE). Thermal analysis, evolved gas analysis (TGA-FTIR), flammability tests (LOI, UL94), microcombustion calorimeter (MCC) and chemical analyses of residues (SEM-EDX) were used. Alcpp provides TPEE with desired flame retardancy and anti-dripping property and shows a good compatibility with TPEE. TGA-FTIR and SEM-EDX analysis show that Alcpp can depress the heating release and promote the char forming and acts mainly in condensed phase. In addition, Alcpp combining with MPP achieves better fire-resistant performance than Alcpp alone. When total additives is kept 28 wt%, 25 wt% Alcpp combining 3 wt% MPP exhibits the optimum synergy by increasing char yield and depressing heat release and flammability. The reason for the synergy is due to a strong compact carbonaceous char resulting from reaction between Alcpp and MPP, which effectively prevent the dripping of the TPEE during combustion.

Occurrence of agrochemical residues in beeswax samples collected in Italy during 2013–2015

Considering the importance of honey bees for pollination activity and biodiversity preservation different studies have dealt with the impact of pesticides on honeybee health. Within the hive, beeswax is a matrix of particular interest because most of the chemicals used in agricultural and beekeeping activities can easily accumulate and persist in this matrix long after treatment has ceased, affecting honeybees survival. However, chemical analyses of pesticide residues in beeswax are not mandatory, so there are no residue limits, for beeswax. The present study was carried out with the aim of investigating the beeswax residue pattern in the Italian hives. 178 beeswax samples collected from 2013 to 2015 were analyzed for 247 pesticides. 73.6% of the analyzed samples reported the presence of one or more pesticides. On average every single sample showed a mean of three different pesticides each with a maximum of fourteen compounds, some of which were banned in Europe or not authorized in Italy. The higher frequencies were associated with three acaricides: coumaphos (60.7% of samples), tau-fluvalinate (50%) and chlorphenvinphos (35.4%), but the higher concentrations were associated to pyrethrins and piperonil butoxide.

Residue analysis of smoking pipe fragments from the Feltus archaeological site, Southeastern North America

The practice of pipe smoking was commonplace among indigenous cultures of the Eastern Woodlands of North America. However, many questions remain concerning what materials were smoked and when tobacco first became a part of this smoking tradition. Chemical analysis of organic residues extracted from archaeological smoking pipes is an encouraging avenue of research into answering questions regarding the development of a smoking complex within indigenous cultures of the Eastern Woodlands. In the right environmental conditions, absorbed organic compounds within artifacts can remain structurally stable for millennia, allowing analyses of organic matter to be performed on relics of advanced age. In this study, organic matter from six pipe fragments derived from the prehistoric Feltus site in Mississippi was extracted and analyzed via GC-MS, a process that allows for the identification of compounds in a complex mixture. Preliminary experiments tested the effects of pH on the efficacy of our extraction solvent to maximize the detectability of alkaloids such as nicotine. Several notable compounds were identified, including nicotine, which serves as a biomarker for tobacco.

Chemical analyses of Egyptian mummification balms and organic residues from storage jars dated from the Old Kingdom to the Copto-Byzantine period

Twenty three samples of Egyptian organic materials, spanning from the Old Kingdom to the Copto-Byzantine Period, were investigated by gas chromatography-mass spectrometry. The sample set was comprised of ten balm samples from human mummies, three balms from shrews, and ten samples of residues scraped from jars and amphora from storehouses.This research program was undertaken with two main goals:Firstly to provide complementary data on the mummification balms from both humans and animals with an emphasis on the occurrence of bitumen in mummification mixtures.Secondly to explore whether the jar residues were mixtures that were used for mummification purposes or whether they were pure ingredients stored for various uses including ritual practices.The analysis highlighted that the most abundant constituents of the mummification balms were: fats or oils, waxes, conifer resin, pitch, mastic resin, castor oil, and bitumen. Balms from animal mummies were not found to be significantly different from the balms from human mummies. Residues from potsherds appeared to belong to two categories: pure products (fats and castor oil) and mixtures containing fats, Pinaceae resin and pitch, mastic resin, and castor oil, i.e. the constituents also identified in mummification balms. The mixtures were thus residues of preparations for ritual practices and embalming.This study demonstrates that bitumen is underestimated by the chemical approach currently applied in most archaeometric studies of Egyptian organic residues, which are better suited for the identification of lipids and resinous materials. We thus applied a specific analytical design, targeted at bitumen. Bitumen from the Dead Sea was conclusively identified using as reference materials for comparison, i.e. the present day bitumen from the Dead Sea floating blocks, as well as several bitumens from mummification balms and bitumen lumps unearthed from the archaeological site of Tell Yarmouth near Jerusalem in Israel.

Pottery use by early Holocene hunter-gatherers of the Korean peninsula closely linked with the exploitation of marine resources

The earliest pottery on the Korean peninsula dates to the early Holocene, notably later than other regions of East Asia, such as Japan, the Russian Far East and Southern China. To shed light on the function of such early Korean pottery and to understand the motivations for its adoption, organic residue analysis was conducted on pottery sherds and adhered surface deposit on the wall of pottery vessels (foodcrusts) excavated from the Sejuk shell midden (7.7–6.8ka calBP) on the southeastern coast and the Jukbyeon-ri site (7.9–6.9ka calBP) on the eastern coast of the Korean peninsula, that represents the earliest pottery assemblages with reliable radiocarbon dates. Through chemical and isotopic residue analysis, we conclude that the use of pottery at these sites was oriented towards marine resources, supported by lipid biomarkers typical of aquatic organisms and stable carbon isotope values that matched authentic marine reference fats. The findings contrast with other archaeological evidence, which shows that a wider range of available food resources were exploited. Therefore, we conclude pottery was used selectively for processing aquatic organisms perhaps including the rendering of aquatic oils for storage. Early pottery use in Korea is broadly similar to other prehistoric temperate hunter-gatherers, such as in Japan, northern Europe and northern America. However, it is also notable that elaborately decorated red burnished pottery excavated from isolated location at the Jukbyeon-ri site had a different usage pattern, which indicates that division of pottery use by vessel form was established even at this early stage.