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This study is focused on the development of analytical methods for characterization of printed circuit boards (PCBs) from mobile phones by direct analysis using three complementary spectroanalytical techniques: laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS), laser-induced breakdown spectroscopy (LIBS), and micro X-ray fluorescence spectroscopy (micro-XRF). These techniques were combined with principal component analysis (PCA) to investigate the chemical composition on the surface and depth profiling of PCB samples. The spatial distribution of important base metals (e.g. Al, Au, Ba, Cu, Fe, Mg, Ni, Zn), toxic elements (e.g. Cd, Cr, Pb) as well as the non-metallic fraction (e.g. P, S and Si) from conductive tracks, solder mask and integrated components were detected within the PCB samples. Univariate and multivariate approaches were also performed to obtain calibration models for Cu determination. The results were compared to reference concentrations obtained by inductively coupled plasma-optical emission spectrometry (ICP-OES) after microwave-assisted acid leaching using aqua regia. To this end, two PCB samples (50 × 34 mm2) were cut into small parts of 40 subsamples (10 × 8.5 mm2) and analyzed by ICP-OES and the Cu concentrations ranged from 13 to 45% m m-1. Partial least squares (PLS) regression was used to data fusion of analytical information from LIBS and micro-XRF analysis. The proposed calibration methods for LIBS and micro-XRF were tested for the 40 PCB subsamples, in which the best results were obtained combining both data sources though a low-level data fusion. Root mean square error of cross validation (RMSEC) and recoveries were 3.23% m m-1 and 81-119% using leave-one-out cross validation.
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OBJECTIVES: This study explores whether ancient Atacama Desert populations in northern Chile were exposed to endemic boron contamination. MATERIALS AND METHODS: Using Laser Ablation-Inductively Coupled Plasma-Mass Spectrometry (LA-ICP-MS), we studied 144 strands of ancient mummy hair, ranging from 3000 B.C. to 1500 A.D., excavated from the Lluta, Azapa, and Camarones valleys in northern Chile. We tested whether these ancient populations showed signs of significant boron concentration in hair tissue. RESULTS: On average, all individuals from these valleys showed high boron concentrations, ranging from 1.5 to 4 times above the average boron concentration in contemporary hair (baseline <0.85 µg/g). The boron concentration in mummy hair varied according to the main geographic areas mentioned above. CONCLUSIONS: The rivers of northern Chile have high geogenic boron concentrations. They contain 38 times above the recommended limit for human consumption. Geogenic boron contamination likely played a role in population morbidity and the types of crops that were cultivated in antiquity. The ancient populations were chronically affected by boron overexposure, suggesting that ancient geogenic water contamination should be considered when discussing the biocultural trajectories of ancient populations.
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Boro/análisis , Exposición a Riesgos Ambientales/análisis , Adolescente , Adulto , Niño , Preescolar , Chile , Clima Desértico , Femenino , Cabello/química , Historia Antigua , Humanos , Lactante , Recién Nacido , Masculino , Persona de Mediana Edad , Momias/historia , Ríos/química , Adulto JovenRESUMEN
This article describes the hidden natural chemical contaminants present in a unique desert environment and their health consequences on ancient populations. Currently, millions of people are affected worldwide by toxic elements such as arsenic. Using data gathered from Atacama Desert mummies, we discuss long-term exposure and biocultural adaptation to toxic elements. The rivers that bring life to the Atacama Desert are paradoxically laden with arsenic and other minerals that are invisible and tasteless. High intake of these toxic elements results in severe health and behavioral problems, and even death. We demonstrate that Inca colonies, from Camarones 9 site, were significantly affected by chemical contaminants in their food and water. It appears however, some modern-day Andean populations resist the elevated levels of arsenic exposure as a result of positive selection mediated via the arsenic methyltransferase enzyme and display more tolerance to high chemical doses. This article further debate the effects of natural pollution and biocultural adaptation of past populations.
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Intoxicación por Arsénico , Exposición a Riesgos Ambientales , Arqueología , Arsénico/análisis , Arsénico/metabolismo , Niño , Humanos , Momias , Polidactilia , Enfermedades de la Piel , América del SurRESUMEN
The use of propellant for making improvised explosive devices (IED) is an incipient criminal practice. Propellant can be used as initiator in explosive mixtures along with other components such as coal, ammonium nitrate, sulfur, etc. The identification of the propellant's brand used in homemade explosives can provide additional forensic information of this evidence. In this work, four of the most common propellant brands were characterized by Fourier-transform infrared photoacoustic spectroscopy (FTIR-PAS) which is a non-destructive micro-analytical technique. Spectra shows characteristic signals of typical compounds in the propellants, such as nitrocellulose, nitroglycerin, guanidine, diphenylamine, etc. The differentiation of propellant components was achieved by using FTIR-PAS combined with chemometric methods of classification. Principal component analysis (PCA) and soft independent modelling of class analogy (SIMCA) were used to achieve an effective differentiation and classification (100%) of propellant brands. Furthermore, propellant brand differentiation was also assessed using partial least squares discriminant analyses (PLS-DA) by leave one out cross (â¼97%) and external (â¼100%) validation method. Our results show the ability of FTIR-PAS combined with chemometric analysis to identify and differentiate propellant brands in different explosive formulations of IED.
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Biodegradation of tributyltin (TBT) by four tin resistant Gram negative bacteria isolated from extremely contaminated river sediments in the Atacama Desert in Chile was studied. Moraxella osloensis showed the greatest resistance and degradation capability of TBT, producing less toxic by-products, such as dibutyltin (DBT) and inorganic tin. In 7 days, approximately 80 % of TBT degradation was achieved, generating close to 20 % of DBT as degradation product. The degradation rate constant (k) was 0.022 [day(-1)] and TBT half-life (t1/2) in culture was 4.3 days. Debutylation is stated a probable mechanism of TBT degradation.
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Bacterias/metabolismo , Clima Desértico , Compuestos Orgánicos de Estaño/análisis , Estaño/análisis , Compuestos de Trialquiltina/análisis , Alcaligenes/metabolismo , Biodegradación Ambiental , Burkholderia cepacia/metabolismo , Chile , Farmacorresistencia Bacteriana , Sedimentos Geológicos/química , Semivida , Moraxella/metabolismo , Pseudomonas/metabolismo , Ríos , Suelo , Microbiología del Suelo , Contaminantes del Suelo/análisis , Factores de Tiempo , Contaminantes del Agua/análisis , Yersinia/metabolismoRESUMEN
Ethnic groups from the Atacama Desert (known as Atacameños) have been exposed to natural arsenic pollution for over 5000 years. This work presents an integral study that characterizes arsenic species in water used for human consumption. It also describes the metabolism and arsenic elimination through urine in a chronically exposed population in northern Chile. In this region, water contained total arsenic concentrations up to 1250 µg L(-1), which was almost exclusively As(V). It is also important that this water was ingested directly from natural water sources without any treatment. The ingested arsenic was extensively methylated. In urine 93% of the arsenic was found as methylated arsenic species, such as monomethylarsonic acid [MMA(V)] and dimethylarsinic acid [DMA(V)]. The original ingested inorganic species [As(V)], represent less than 1% of the total urinary arsenic. Methylation activity among individuals can be assessed by measuring primary [inorganic As/methylated As] and secondary methylation [MMA/DMA] indexes. Both methylation indexes were 0.06, indicating a high biological converting capability of As(V) into MMA and then MMA into DMA, compared with the control population and other arsenic exposed populations previously reported.
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Arsénico/orina , Agua Potable/química , Contaminantes Químicos del Agua/orina , Arsénico/toxicidad , Arsenicales/orina , Ácido Cacodílico/orina , Chile , Agua Potable/normas , Monitoreo del Ambiente , Etnicidad , Humanos , Metilación , Contaminantes Químicos del Agua/toxicidad , Calidad del AguaRESUMEN
Microspatial analyses of the trace element composition of dental enamel are made possible using laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). Fine spatial resolution, multielement capabilities, and minimal sample destruction make this technique particularly well-suited for documenting the distribution of elements in sequentially calcifying layers of enamel. Because deciduous enamel forms from week 13 in utero up to 9 months postnatally (thereafter essentially becoming inert), the application of LA-ICP-MS allows for the retrospective measurement of prenatal and early postnatal trace-element uptake during a critical period of child development. In this study, we compared intra- and intertooth intensities of 25Mg, 57Fe, 66Zn, 68Zn, 88Sr, 138Ba, and 208Pb via LA-ICP-MS of 38 exfoliated deciduous incisors and canines donated by 36 participants in the Solís Valley Mexico Nutrition Collaborative Research Support Program (NCRSP). Pre- and postnatal comparisons within teeth showed significant increases (P < 0.001) and greater variation in the abundance of all isotopes in postnatal enamel, with the exception of a decrease in 25Mg (P < 0.001) and constant values for 88Sr (P = 0.681). Conversely, comparisons by tooth type and mouth quadrant revealed few significant differences between teeth of the same individual. We argue that more variation in the trace element composition of teeth occurs across developmental areas within a tooth than among different teeth of the same person. This study further demonstrates that sequentially calcifying areas of enamel have different chemical concentrations. The results support the use of microspatial analyses of enamel for understanding changes in nutrition, pollution, and residence.