Direct solid sample analysis of low-cost jewelry using spectroanalytical techniques: exploratory chemical data evaluation and metal migration with synthetic sweat.

Humans have used jewelry for a long time. Initially, this habit had religious purposes for individual protection, then it became a compliment accessory to noble appearance until its popularization with production using cheaper and potentially toxic chemical elements. Therefore, the health of people of low social status has been compromised in such a way that a big part of the metals present in these accessories are potentially toxic. In this regard, with the proposition of legislation limiting these elements' concentrations, several analytical techniques have been used to study their determinations; laser-induced breakdown spectroscopy (LIBS) direct analysis of solids has been highlighted in the past years due to many advantages in several areas. In this study, LIBS and energy dispersive X-ray fluorescence (ED-XRF) were implemented in low-cost jewelry analyses. Then, an exploratory data analysis was carried out using chemometric tools. Finally, the migration of these elements to synthetic sweat was studied to verify its contact with human organisms, and inductively coupled plasma optical emission spectrometry (ICP OES) was employed for the determination of Al, Cd, Cr, Cu, Fe, Mg, Mn, Ni, Pb, Sb, Sn, and Zn.

Direct Determination of Ca, K, and Mg in Soy Leaf Samples Using Laser-Induced Breakdown Spectroscopy.

This study was dedicated to developing analytical methods for determining macronutrients (Ca, K, and Mg) in soy leaf samples with and without petioles. The study's primary purpose was to present Laser-induced breakdown spectroscopy (LIBS) as a viable alternative for directly analyzing leaf samples using chemometric tools to interpret the data obtained. The instrumental condition chosen for LIBS was 70 mJ of laser pulse energy, 1.0 µs of delay time, and 100 µm of spot size, which was applied to 896 samples: 305 of soy without petioles and 591 of soy with petioles. The reference values of the analytes for the proposition of calibration models were obtained using inductively coupled plasma optical emission spectroscopy (ICP-OES) technique. Twelve normalization modes and two calibration strategies were tested to minimize signal variations and sample matrix microheterogeneity. The following were studied: multivariate calibration using partial least squares and univariate calibration using the area and height of several selected emission lines. The notable normalization mode for most models was the Euclidean norm. No analyte showed promising results for univariate calibrations. Micronutrients, P and S, were also tested, and no multivariate models presented satisfactory results. The models obtained for Ca, K, and Mg showed good results. The standard error of calibration ranged from 2.3 g/kg for Ca in soy leaves without petioles with two latent variables to 5.0 g/kg for K in soy leaves with petioles with two latent variables.

Analytical and reclamation technologies for identification and recycling of precious materials from waste computer and mobile phones.

Waste electrical and electronic equipment (WEEE) is one of the world's fastest-growing class of waste. WEEE contain a large amount of precious materials that have aroused the interest to develop new recycling technologies. Hence, effective recycling strategies are extremely necessary to promote the proper handling of these materials as well as for environmentally sound recovery of secondary raw resource. This paper reviews important existing methods and emerging technologies in WEEE management, with special emphasis in characterization, extraction and reclamation of precious materials from waste computer and mobile phones. Traditional pyrometallurgical and hydrometallurgical technologies still play a central role in the recovery of metals. More recently, emerging greener recycling technologies using microorganisms (i.e. biometallurgical), plasma arc fusion method and pretreatments (i.e. ultrasound and mechanochemical technologies) combined with other recycling methods (e.g. hydrometallurgical), and using less toxic solvents such as ionic liquids (ILs) and deep eutectic solvents (DESs) have also been attempted to recycle metals from computer and mobile phone scrap. The role of analytical method development, especially using spectroanalytical methods for chemical inspection and e-waste sorting process at industrial applications is also discussed. This confirmed that most direct sampling techniques such as laser-induced breakdown spectroscopy (LIBS) and X-ray fluorescence (XFR) have several advantages over traditional sorting methods including rapid analytical response, without use of chemical reagents or waste generation, and greater reclamation of precious and critical materials in the WEEE stream.

Multiway Calibration Strategies in Laser-Induced Breakdown Spectroscopy: A Proposal.

In this study, a new approach to laser-induced breakdown spectroscopy (LIBS) data modeling using multiway algorithms was investigated. Two case studies, parallel factor analysis (PARAFAC) and unfolded-partial least-squares with residual bilinearization (U-PLS/RBL) algorithms were used in (1) the determination of Al, Cu, and Fe in samples of reference material of printed circuit board (PCB) from electronic waste and (2) the determination of Ca, K, and Mg in samples of a human mineral supplement, where depth was used to obtain multidimensional data in the first case and delay-time in the second. In addition, univariate calibration was applied and compared with the multiway approaches. In all cases, the calibration data set was prepared from salts. PARAFAC showed satisfactory results in the first study, with low prediction errors and good accuracy for most samples, and the U-PLS/RBL algorithm presented the best performance for mineral supplement samples.

Chemical inspection and elemental analysis of electronic waste using data fusion - Application of complementary spectroanalytical techniques.

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.

Forensic analysis of hand-written documents using laser-induced breakdown spectroscopy (LIBS) and chemometrics.

With the use of Laser Induced Breakdown Spectroscopy (LIBS), fast and semi non-destructive elemental analysis of ball-point pen writings has been performed directly from paper surfaces, aiming to obtain maximum differentiation between pens with a minimum number of pulses. The instrumental variables, the delay time, laser pulse energy and number of pulses per point, were evaluated through factorial design and optimum values were obtained through a quadratic regression model. Several atomic emission lines were tested as fingerprints in order to improve the differentiation between the tested inks and the range of 212-228 and 324-328 nm, which corresponds to Cu emission, demonstrated to be the best alternative as a discriminatory factor for two pens of the same color. However, the background contribution of cheque paper limited the multielement profile of the technique. Seventeen different pens were analyzed. Principal Component Analysis (PCA) treatment was used to classify the samples in clusters and to assemble hyperspectral images in order to obtain visual differentiation of the inks in a scores map. The results obtained by LIBS analysis were verified by microwave-assisted digestion of inks and analysis by ICP OES. Lastly, a real situation test was conducted where a forged document was analyzed by the proposed methodology as an alternative to distinguish between two inks of the same color, originating from different pens. For this proof of concept study, seventeen samples were evaluated, but further studies related to heterogeneity between pulses and samples should be carried out.

Direct determination of Al and Pb in waste printed circuit boards (PCB) by laser-induced breakdown spectroscopy (LIBS): Evaluation of calibration strategies and economic - environmental questions.

Matrix-matching calibration (MMC), two-point calibration transfer (TP CT), one-point and multi-line calibration (OP MLC), single-sample calibration (SSC) and calibration free (CF) were evaluated in order to overcome matrix effects in laser-induced breakdown spectroscopy (LIBS). These calibration strategies were evaluated for direct determination of Al and Pb in waste printed circuit boards (PCB) using direct solids analysis by LIBS. Each strategy has limitations and advantages of its implementation, for the correction of matrix effects, so that it allows elementary determination with adequate accuracy. The MMC and CF proved to be excellent calibration strategies for the determination of strategic (Al) and toxic (Pb) elements by LIBS, with good recoveries (ranging from 80-120%) and low relative standard deviation (RSD%) values. A detailed discussion of the advantages and limitations of each of these five calibration strategies evaluated for LIBS is presented in this study. Lead concentrations in waste PCB samples are 5-12 times higher than established by Directive 2011/65/EU, and the samples analyzed contain between 3 and 55 g kg-1 Al, being an interesting economic and recycling source for this metal.

Response surface methodology applied to tropical freshwater treatment.

This paper presents the profits and disadvantages of the chemometrics approach instead of the one-factor-at-a-time (OFAT) coagulation diagram approach for tropical water physicochemical treatment. Central composite design associate to response surface methodology (CCD-RSM) is used to find the real best conditions for coagulant dosage and pH aiming at high-turbidity removal. The number of experiments needed to chemometrics model construction (12) is comparatively smaller than that used in the coagulation diagram (84), saving financial and environmental resources. Arguments for Water Treatment Plants (WTP) considering the replacement of coagulation diagram approach by the CCD-RSM approach in drinking water treatment are presented. Chemometrics models are all constructed on a free software platform, providing the best pH within the range 7.7-8.1, and the best coagulant dosage (polyaluminium chloride, PAC) between 2.0 and 3.1 mg Al2O3 L-1 (equivalent in mass). CCD-RSM provides a faster, lower-cost and more reliable alternative tool for WTP decision-making instead of the OFAT model, mainly for waters more affected by seasonal effects as can be seen in tropical and subtropical countries.

Calibration strategies for the direct determination of rare earth elements in hard disk magnets using laser-induced breakdown spectroscopy.

This study is dedicated to the direct determination of base (B and Fe) and some rare earth elements (REE; Dy, Gd, Nd, Pr, Sm and Tb) in hard disk magnets. Five calibration strategies were tested and compared. Two of them are related to multivariate calibration: multiple linear regression (MLR) and partial least squares (PLS). Both presented adequate trueness values within a range of 80-120% for almost all analytes. The only exception was Tb, which was probably due to matrix effects. The use of MLR and PLS permits the testing of calibration models in the presence of interference, but matrix effects are not corrected. Because of this, three other univariate calibration methods were also tested and compared: multi-energy calibration (MEC), one-point gravimetric standard addition (OP GSA) and two-point calibration transfer (TP CT). These three calibration approaches permit matrix effects corrections, but an appropriate selection of the blank and standard is mandatory. The standard error obtained ranged from 0.01 to 6% using these univariate calibration methods.

Microwave-assisted digestion using dilute nitric acid solution and investigation of calibration strategies for determination of As, Cd, Hg and Pb in dietary supplements using ICP-MS.

This study proposes an analytical procedure for microwave-assisted sample preparation of dietary supplements for athletes using dilute nitric acid solution followed by determination of elemental impurities (As, Cd, Hg and Pb) by inductively coupled plasma mass spectrometry (ICP-MS) according to the United States Pharmacopeia Chapters 2232 and 233. Calibration strategies as internal standardization (IS), multi-isotope calibration (MICal), and one-point standard addition (OP SA) were applied for correction of matrix effects. The optimization of the sample preparation procedure was performed using Doehlert experimental design based on overall desirability results (residual acidity, dissolved organic carbon and recoveries reached for certified reference material of Typical Diet) for each calibration method evaluated. Accuracy was also evaluated by recovery experiments according to the permissible daily exposure specific for each element and samples were spiked with element concentrations of 0.5J and 1.5J in order to check accuracies for As, Cd, Hg and Pb. Recoveries ranged from 82 to 120% using IS, 90 to 125% using MICal, 88 to 120% using OP SA and the repeatability was demonstrated by a precision lower than 10% RSD. Ten samples of dietary sport supplements were analyzed using the three calibration methods evaluated and the concentrations of As, Cd and Pb determined in eight samples were lower than the limits established by the Chapter 2232.

Past and emerging topics related to electronic waste management: top countries, trends, and perspectives.

A bibliometric analysis was performed to assess historical and recent research trends regarding e-waste studies from 1998 to 2018. Documents related to e-waste were identified from the Clarivate Analytics Web of Science© (WoS) database, and a total of 3311 academic articles was retrieved. The analysis was performed from four main aspects: (1) publication activity by year, by WoS category, and by geographic distribution; (2) journals; (3) most-cited papers; and (4) top 10 countries and author keyword analysis. The number of publications concerning e-waste issues has increased substantially over the last 20 years, especially in the environmental science category, and more than a third of the publications were produced in China (1181 records). Waste Management and Environmental Science & Technology were the most sought-after journals for disseminating the results. Studies related to "e-waste flow analysis," "recycling," "recovery of precious metals," and "risk assessment of recycling areas" have been the most common for several years. The analysis of keywords suggested that there are many topics on electronic waste and that each country has presented a different focus of research. Overall, the bibliometric analysis proved to be an efficient tool with which to monitor historical and current research trends and to evaluate the sheer volume of currently existing scientific literature on e-waste topics.

Calibration strategies for determination of the In content in discarded liquid crystal displays (LCD) from mobile phones using laser-induced breakdown spectroscopy (LIBS).

Mobile phones are one of the fastest growing types of electronic waste disposed of world-wide. One of the main components in these devices is the LCD (liquid crystal display) panel that contains conductive electrodes made of indium tin oxide. A large amount of In, which is categorized as a critical raw element, has been used to manufacture indium tin oxide films. This study applies laser-induced breakdown spectroscopy (LIBS) for the analysis of LCD samples from mobile phones in order to determine the In content. Both conventional univariate calibration and non-traditional calibration using different transition energies (emission lines), named multi-energy calibration (MEC), were assessed. To evaluate the accuracy of the results, Method EPA 3052 was performed for acid digestion of the samples using microwave-assistance, and the In content was determined by ICP OES. Indium concentrations ranged from 35 to 47 mg kg-1 for all samples evaluated. The results showed the best accuracy for LIBS methods after the spectra were normalized by the carbon line at 193.09 nm. The univariate-LIBS model showed a standard error of calibration (SEC) about 10-fold lower than the samples' concentration, LOD and LOQ of 0.3 and 1.0 mg kg-1, respectively. MEC proved to be a fast and efficient alternative for direct solid analysis, and In concentrations were determined by LIBS using only two calibration pellets. The LOD and LOQ for MEC-LIBS method were 2.1 and 7 mg kg-1, respectively.

Application of Multi-energy Calibration for Determination of Chromium and Nickel in Nickeliferous Ores by Laser-induced Breakdown Spectroscopy.

A multi-energy calibration method was applied for the determination of chromium and nickel in nickeliferous ores by laser-induced breakdown spectroscopy. For the optimization of the laser-induced breakdown spectroscopy parameters, such as laser fluence and delay time, an experimental study was conducted. The best results in terms of trueness were observed using a laser fluence and a delay time of 2500 J/cm2 and 1.1 µs, respectively. A study of sample matrix effects and the determination of emission lines for calibration and normalization of the spectra were undertaken, and appropriate values of those variables were selected for each analyte. The trueness values for chromium and nickel varied from 89 to 114% when certified reference samples (nickeliferous laterite, rock phosphate and contaminated soil) were analyzed.

Direct determination of Ca, K, Mg, Na, P, S, Fe and Zn in bivalve mollusks by wavelength dispersive X-ray fluorescence (WDXRF) and laser-induced breakdown spectroscopy (LIBS).

This study aims to develop methods for determination of Ca, K, Mg and Na by laser-induced breakdown spectroscopy (LIBS) and Ca, K, Mg, Na, P, S, Fe and Zn by wavelength dispersive X-ray fluorescence (WDXRF) in pressed pellets bivalve mollusks. LIBS and WDXRF calibration models were built with references values determined by inductively coupled plasma optical emission spectrometry (ICP OES) after acid digestion. The calibration models for LIBS and WDXRF were obtained from 28 samples (14 for calibration and 14 for validation). It was possible to implement a validation between LIBS and WDXRF methods for elements Ca, K, Mg and Na. The proposed calibration model obtained using LIBS and WDXRF data presented a good correlation with reference values obtained by ICP OES.

Determination of toxic metals in leather by wavelength dispersive X-ray fluorescence (WDXRF) and inductively coupled plasma optical emission spectrometry (ICP OES) with emphasis on chromium.

The tanning industry is one of the largest environmental polluters due to high generation waste in all production processes, but the tanning is particularly worrisome due to the use of significant amounts of chromium. Cr is an element potentially toxic to both health and the environment, depending on the concentration and the oxidation state. Cr(VI) can come in contact with human skin when using leather goods, which can cause allergies and dermatitis, besides being carcinogenic. Considering that approximately 90% of the world production of leather is performed with Cr salts, the determination of this element in leather is necessary to avoid exposure to the risks that the element can provide. The main goal of this study was the development of an alternative analytical method for the determination of Cr in leathers (ovine and bovine leather tanned with Cr and vegetable tannin) using wavelength dispersive X-ray fluorescence (WDXRF) for direct solid analysis. Besides performing analysis of the chemical composition and determination of Al, As, Ba, Ca, Cd, Cr, Cu, Fe, Mg, Ni, Pb, Sb, Sr, Ti, and Zn in leather by inductively coupled plasma optical emission spectrometry (ICP OES). Principal component analysis (PCA) was also used in the evaluation of the WDXRF and ICP OES data sets. WDXRF calibration models for Cr presented satisfactory figures of merit and the analysis of the leathers revealed an alarming concentration of total Cr in the samples reaching 21,353 mg kg-1.

Spectroanalytical method for evaluating the technological elements composition of magnets from computer hard disks.

In this study, inductively coupled plasma optical emission spectrometry (ICP OES) was used for the development of an analytical procedure for elemental analysis of hard disks (HDs). More than 50 samples were acquired and separated according to the manufacturers. Both magnets were used, namely, the actuator (a) and the spindle (s) motor. The samples were heated to remove magnetism, ground in a knife mill and sieved. Different digestion procedures were performed with a block digester and microwave, and three acid concentrations were employed. Due to the lack of certified materials or references from HDs, tests of standard addition and recovery were performed to verify the accuracy of the proposed method. Hyperspectral image and principal component analysis were also used to assist in the data treatment related to the Ni layer. For both magnets, the best analytical procedure was 100 mg of sample, 7 mol L-1 nitric acid and a digester block. The elements observed in the highest concentrations were Fe followed by Nd and Pr. This procedure was simpler than others were and prioritized the principles of green chemistry.

Evaluation of the Chemical Composition of Synthetic Leather Using Spectroscopy Techniques.

Synthetic leather samples from Brazil and Paraguay were evaluated in this study using three spectroscopy techniques: inductively coupled plasma optical emission spectrometry (ICP-OES), laser-induced breakdown spectroscopy (LIBS), and wavelength dispersive X-ray fluorescence (WDXRF). The obtained information from each technique was separately inspected with principal component analysis (PCA). The concentrations of the elements determined in the synthetic leathers using ICP-OES decreased in the following order: Ca > Cr > Mg > Ba > Pb > Al > Fe > Zn > Sb > Ni with a concentration range below the limit of quantification (

Determination of Elemental Content in Solder Mask Samples Used in Printed Circuit Boards Using Different Spectroanalytical Techniques.

Solder masks are essential materials used in the manufacture of printed circuit boards (PCB). This material protects PCBs against several types of damage and performance failure. In this study, the capabilities of laser-induced breakdown spectroscopy (LIBS) were investigated for the direct analysis of solder masks typically commercialized for homemade PCB production, and inductively coupled plasma-optical emission spectrometry (ICP-OES) was used to obtain a chemical profile for the target analytes Al, As, Ba, Cd, Co, Cr, Cu, Fe, Hg, Mg, Mn, Ni, Pb, Sb, Sn, and Zn. Inductively coupled plasma-mass spectrometry (ICP-MS) was also employed for the determination of potentially toxic elements, such as As, Cd, Cr, Pb, and Hg. In addition to the qualitative information that may be useful for obtaining the spectral profile related to the raw materials present in solder masks formulations, LIBS was also applied for major elements (Al, Ba, Cu, Fe, Mg, and Zn) determination, but due to the low sensitivity, the obtained results were only semi-quantitative for Ba. Regarding Cd, Cr, Hg, and Pb, the samples analyzed were following the restriction of hazardous substances (RoHS) directive of the European Union.

Use of laser-induced breakdown spectroscopy for the determination of polycarbonate (PC) and acrylonitrile-butadiene-styrene (ABS) concentrations in PC/ABS plastics from e-waste.

Due to the continual increase in waste generated from electronic devices, the management of plastics, which represents between 10 and 30% by weight of waste electrical and electronic equipment (WEEE or e-waste), becomes indispensable in terms of environmental and economic impacts. Considering the importance of acrylonitrile-butadiene-styrene (ABS), polycarbonate (PC), and their blends in the electronics and other industries, this study presents a new application of laser-induced breakdown spectroscopy (LIBS) for the fast and direct determination of PC and ABS concentrations in blends of these plastics obtained from samples of e-waste. From the LIBS spectra acquired for the PC/ABS blend, multivariate calibration models were built using partial least squares (PLS) regression. In general, it was possible to infer that the relative errors between the theoretical or reference and predicted values for the spiked samples were lower than 10%.

Calibration strategies for the direct determination of Ca, K, and Mg in commercial samples of powdered milk and solid dietary supplements using laser-induced breakdown spectroscopy (LIBS).

This study describes the application of laser-induced breakdown spectroscopy (LIBS) for the direct determination of Ca, K and Mg in powdered milk and solid dietary supplements. The following two calibration strategies were applied: (i) use of the samples to calculate calibration models (milk) and (ii) use of sample mixtures (supplements) to obtain a calibration curve. In both cases, reference values obtained from inductively coupled plasma optical emission spectroscopy (ICP OES) after acid digestion were used. The emission line selection from LIBS spectra was accomplished by analysing the regression coefficients of partial least squares (PLS) regression models, and wavelengths of 534.947, 766.490 and 285.213nm were chosen for Ca, K and Mg, respectively. In the case of the determination of Ca in supplements, it was necessary to perform a dilution (10-fold) of the standards and samples to minimize matrix interference. The average accuracy for powdered milk ranged from 60% to 168% for Ca, 77% to 152% for K and 76% to 131% for Mg. In the case of dietary supplements, standard error of prediction (SEP) varied from 295 (Mg) to 3782mgkg-1 (Ca). The proposed method presented an analytical frequency of around 60 samples per hour and the step of sample manipulation was drastically reduced, with no generation of toxic chemical residues.