3D-printed portable device for illicit drug identification based on smartphone-imaging and artificial neural networks.

In this manuscript, a 3D-printed analytical device has been successfully developed to classify illicit drugs using smartphone-based colorimetry. Representative compounds of different families, including cocaine, 3,4-methylenedioxy-methamphetamine (MDMA), amphetamine and cathinone derivatives, pyrrolidine cathinones, and 3,4-methylenedioxy cathinones, have been analyzed and classified after appropriate reaction with Marquis, gallic acid, sulfuric acid, Simon and Scott reagents. A picture of the colored products was acquired using a smartphone, and the corrected RGB values were used as input data in the chemometric treatment. ANN using two active layers of nodes (6 nodes in layer 1 and 2 nodes in layer 2) with a sigmoidal transfer function and a minimum strict threshold of 0.50 identified illicit drug samples with a sensitivity higher than 83.4 % and a specificity of 100 % with limits of detection in the microgram range. The 3D printed device can operate connected to a rechargeable lithium-ion cell portable battery, is inexpensive, and requires minimal training. The analytical device has been able to discriminate the analyzed psychoactive substances from cutting and mixing agents, being a useful tool for law enforcement agents to use as a screening method.

Partial least squares modelization of energy dispersive X-ray fluorescence.

As a proof of concept, a green methodology has been developed for the energy dispersive X-ray fluorescence (ED-XRF) determination of calcium, potassium, iron, magnesium, aluminum, chromium, strontium, phosphorus and nickel in the peel of untreated kaki fruit (Diospyros kaki. L) samples. ED-XRF spectra of fifty-six kakis purchased in the local area of LLombay (Valencia) were obtained directly from samples without any previous treatment and without sample damage just after cleaning the fruit with distilled water. Inductively Couple Plasma Optical Emission Spectrometry (ICP-OES) was used as a reference method to determine the mineral elements after microwave assisted acid digestion. XRF spectra and concentration values obtained by ICP-OES were processed using partial least squares (PLS) data treatment to build the corresponding chemometric models for prediction of mineral profile of samples. PLS-ED-XRF permits a direct and accurate determination of Ca and K in kaki peel. For Al, Fe, Mg, Ni and Sr screening semiquantitative results were obtained. Concentrations obtained directly by the internal calibration of instrument, using GeoChem Trace model, were also compared with data predicted by chemometric models being found that PLS models must replace the calibration of the instrument for thus kind of analysis.

Direct determination by portable ED-XRF of mineral profile in cocoa powder samples.

The present study has exploited the rapidity of the analysis and the multi-elemental capability of the energy dispersive X- ray fluorescence (ED-XRF) technique for the mineral profile determination in cocoa powder. A fast, cheap and environmental sustainable method without reagent consumption or toxic waste generation has been proposed. The samples can be prepared in the form of pellets of 13 mm in diameter and 2-3 mm thickness. The different internal calibrations used by ED-XRF equipment did not provide accurate results when comparing the mineral profile with the concentration obtained by Inductively Couple Plasma Optical Emission Spectroscopy (ICP-OES) after microwave assisted digestion of samples. For direct ED-XRF analysis of the cocoa samples, an external calibration using as standards the cocoa samples diluted with sugar was prepared. The analytical parameters of Relative Standard Deviation and Limit of Detection for the determined elements are adequate to the concentration levels found in the samples.

Evaluation of the Content of Antimony, Arsenic, Bismuth, Selenium, Tellurium and Their Inorganic Forms in Commercially Baby Foods.

Baby foods, from the Spanish market and prepared from meat, fish, vegetables, cereals, legumes, and fruits, were analyzed to obtain the concentration of antimony (Sb), arsenic (As), bismuth (Bi), and tellurium (Te) as toxic elements and selenium (Se) as essential element. An analytical procedure was employed based on atomic fluorescence spectroscopy which allowed to obtain accurate data at low levels of concentration. Values of 14 commercial samples, expressed in nanograms per gram fresh weight, ranged for Sb 0.66-6.9, As 4.5-242, Te 1.35-2.94, Bi 2.18-4.79, and Se 5.4-109. Additionally, speciation studies were performed based on data from a non-chromatographic screening method. It was concluded that tellurium and bismuth were mainly present as inorganic forms and selenium as organic form, and antimony and arsenic species depend on the ingredients of each baby food. Risk assessment considerations were made by comparing dietary intake of the aforementioned elements through the consumption of one baby food portion a day and recommended or tolerable guideline values.

Prediction of organic carbon and total nitrogen contents in organic wastes and their composts by Infrared spectroscopy and partial least square regression.

Middle and near infrared (MIR and NIR) were employed to determine organic carbon (OC) and total nitrogen (TN) in different soil organic amendments including wastes, composts and mixtures of composts and organic wastes. Prediction models based on partial least squares (PLS) regression from the spectra of untreated samples were built. Different spectra preprocessing strategies were adopted and the best number of latent variable was evaluated using leave-one-out cross-validation. Attenuated total reflectance (PLS-ATR-MIR) and diffuse reflectance (PLS-DR-NIR) models were built and evaluated from root mean square error of cross validation and prediction (RMSECV and RMSEP), coefficients of determination for prediction (R2 pred) and residual predictive deviation (RPD). ATR-MIR provided a better prediction capability than DR-NIR with RMSEP, R2pred and RPD values of 2.2%, 0.76 and 2.0 for OC and values of 0.2%, 0.82 and 2.4 for TN, respectively.

Determination of total phenolic compounds in compost by infrared spectroscopy.

Middle and near infrared (MIR and NIR) were applied to determine the total phenolic compounds (TPC) content in compost samples based on models built by using partial least squares (PLS) regression. The multiplicative scatter correction, standard normal variate and first derivative were employed as spectra pretreatment, and the number of latent variable were optimized by leave-one-out cross-validation. The performance of PLS-ATR-MIR and PLS-DR-NIR models was evaluated according to root mean square error of cross validation and prediction (RMSECV and RMSEP), the coefficient of determination for prediction (Rpred(2)) and residual predictive deviation (RPD) being obtained for this latter values of 5.83 and 8.26 for MIR and NIR, respectively.

Authentication of Alicante's Mountain cherries protected designation of origin by their mineral profile.

Chemometric analysis of inductively coupled plasma optical emission spectroscopy (ICP-OES) data was employed to verify the origin of cherry samples of different areas of Spain: Aragón, Cáceres, Castellón, Huesca and Alicante's Mountain Protected Geographic Indication (PGI). The ability of multivariate analysis methods, such as discriminant analysis (DA), was used to achieve cherry classification from their mineral content. The study was performed using 22 variables (concentrations of Al, As, B, Ba, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, K, Mg, Mn, Na, Ni, Pb, Se, Sr, Ti and Te) and 23 variables (concentrations of Al, As, B, Ba, Be, Bi, Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mo, Na, Ni, Pb, Se, Sr, Ti, Tl and V), for cherry stone and edible part, respectively, and the best discrimination was found on using edible part mineral composition which permits a correct classification of 100% of the considered samples.

Fast determination of fish mineral profile. Application to Vietnamese panga fish.

A methodology, based on inductively coupled plasma optical emission spectrometry after microwave-assisted digestion with HNO3/H2O2, was developed to determine the mineral profile of panga fish samples imported from Vietnam. A total of 42 essential and toxic elements were studied in seven samples taken from the local market. Preliminary studies were focused on selecting the best wavelength and the required dilution of samples in order to provide the highest sensitivity to maximize the number of analytes to be determined without spectral or matrix interferences. Adequate accuracy was assured by the analysis of certified reference material TORT-2. Mercury was also determined by a direct method based on atomic absorption spectrometry. Results obtained indicated a low mineral profile, fourteen elements were found at quantitatively levels, Na (6000 µg g(-1)) K (1800 µg g(-1)) Mg (173 µg g(-1)), Ca (80 µg g(-1)), Zn (2.44 µg g(-1)), Fe (1.6 µg g(-1)), Al (1.1 µg g(-1)), Sr (0.4 µg g(-1)) and B, Ba, Hg, Mn, V (under 0.1 µg g(-1)). Additionally data were compared with those previously reported in literature and an estimation of daily intake was calculated and compared with recommended or tolerable guidelines values. Levels of As, Cd, Pb and Hg were far below the established values by the European Community.

Determination of total Sb, Se, Te, and Bi and evaluation of their inorganic species in garlic by hydride-generation-atomic-fluorescence spectrometry.

A sensitive and simple analytical method has been developed for determination of Sb(III), Sb(V), Se(IV), Se(VI), Te(IV), Te(VI), and Bi(III) in garlic samples by using hydride-generation-atomic-fluorescence spectrometry (HG-AFS). The method is based on a single extraction of the inorganic species by sonication at room temperature with 1 mol L(-1) H2SO4 and washing of the solid phase with 0.1% (w/v) EDTA, followed by measurement of the corresponding hydrides generated under two different experimental conditions directly and after a pre-reduction step. The limit of detection of the method was 0.7 ng g(-1) for Sb(III), 1.0 ng g(-1) for Sb(V), 1.3 ng g(-1) for Se(IV), 1.0 ng g(-1) for Se(VI), 1.1 ng g(-1) for Te(IV), 0.5 ng g(-1) for Te(VI), and 0.9 ng g(-1) for Bi(III), in all cases expressed in terms of sample dry weight.

A review of non-chromatographic methods for speciation analysis.

This manuscript overviews relevant scientific literature concerning speciation of trace elements by using non-chromatographic methods. The main principles of the different strategies proposed in the published works and their advantages and drawbacks are discussed in order to provide to the readers an appropriate picture of the state-of the-art of fast and cheap methodologies available to obtain information about the presence of different chemical forms of trace elements in environmental, clinical and food samples. A selection of the methods proposed for the speciation of the different elements studied was also provided together with their main features.

Chemometric determination of arsenic and lead in untreated powdered red paprika by diffuse reflectance near-infrared spectroscopy.

It has been evaluated the potential of near-infrared (NIR) diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) as a way for non-destructive measurement of trace elements at microg kg(-1) level in foods, with neither physical nor chemical pre-treatment. Predictive models were developed using partial least-square (PLS) multivariate approaches based on first-order derivative spectra. A critical comparison of two spectral pre-treatments, multiplicative signal correction (MSC) and standard normal variate (SNV) was also made. The PLS models built after using SNV provided the best prediction results for the determination of arsenic and lead in powdered red paprika samples. Relative root-mean-square error of prediction (RRMSEP) of 23% for both metals, arsenic and lead, were found in this study using 20 well characterized samples for calibration and 13 additional samples as validation set. Results derived from this study showed that NIR diffuse reflectance spectroscopy combined with the appropriate chemometric tools could be considered as an useful screening tool for a rapid determination of As and Pb at concentration level of the order of hundred microg kg(-1).

Elemental composition of seasoning products.

The elemental composition of seasoning products, like spices garlic and onion, has been reviewed paying special attention to methods proposed in the literature to determine specific elements or as much as possible components of these products which are widespread used in food preservation or food flavouring and can contribute to the intake of both, essential and toxic elements. Sample treatment and metal speciation aspects have been critically revised concerning onion, garlic and pepper (the most commonly studied products).

Monitoring programme on cadmium, lead and mercury in fish and seafood from Valencia, Spain: levels and estimated weekly intake.

The study was carried out to determine the current levels of mercury, cadmium, and lead in fish and seafood from the market of Comunitat Valenciana, Spain. Levels of total mercury ranged from 0.02 to 3.15 mg kg⁻¹ w.w. (average = 0.073 mg kg⁻¹ w.w.). Cadmium concentrations ranged from 0.003 to 0.66 mg kg⁻¹ w.w. (average = 0.27 mg kg⁻¹ w.w.) for seafood, and between 0.003 and 0.71 mg kg⁻¹ w.w. (average = 0.01 mg kg⁻¹ w.w.) for marine fish. Concerning lead, concentrations from 0.02 to 0.36 mg kg⁻¹ w.w (average = 0.04 mg kg⁻¹ w.w.) were found in fish, and from 0.02 to 1.02 mg kg⁻¹ w.w. in seafood (average = 0.147 mg kg⁻¹ w.w.). The levels found were, in general, lower than maximum levels proposed by European legislation. The estimated weekly intake of mercury, cadmium and lead through fish and seafood consumption was found to be about 43%, 10% and 3% of the established provisional tolerable weekly intake, respectively.

ICP-MS multielement determination in fly ash after microwave-assisted digestion of samples.

A microwave assisted digestion procedure has been developed for dissolution of fly ash samples prior to the inductively coupled plasma-mass spectrometric determination of their elemental composition. The developed methodology was validated by carrying out the analysis of two high-silicate containing reference materials (CRM 134R sewage amended soil and NIES JR 1 rock) and by means of the comparison between results found by microwave-assisted digestion and ICP-MS of fly ash samples with those found by neutron activation analysis (NAA) for Sb, Cs, Cr, Co, Fe, U and Zn determination. The method developed can be recommended for routine multielement analysis of fly ash.

Literature survey of on-line elemental speciation in aqueous solutions.

The literature about the on-line speciation in water has been comprehensively studied. Critical examination of this subject reveals that a great deal of work has been performed in this area for inorganic metal species and some organic compounds. The topic studied mainly includes the speciation of chromium, selenium, copper, arsenic, lead, cadmium, mercury, iron, aluminium, nickel, tin, antimony, phosphorus, nitrogen and others. The present literature survey includes also comments about the possibilities and problems of speciation as a function of analytical steps, general strategies involved and methods proposed in the literature for each element or a series of elements.

Mechanism of porous core electroosmotic pump flow injection system and its application to determination of chromium(VI) in waste-water.

An electroosmotic pump flow injection system is introduced in this paper. According to electroosmotic theory, the pump's properties were described. A large flow range (mul min(-1)-ml min(-1)), moderate carrier pressure (>0.15 MPa), reduced performance voltage (<500 V) and stable flow rate (RSD<3.0% in 4 h) are the main properties of the pump. NH(4)OH (0.35 mM) was used as carrier for improving the pump's flow stability. The electroosmotic efficiency of the pump's medium, porous core, can be recovered and regenerated. A sandwich zone was used for sample and reagent introduction in order to adapt to the pump performance. Flow injection-spectrophotometry was employed for the determination of Cr(VI) in waste-water, based on the formation of the complex with 1,5-diphenylcarbazide and absorbance measurement at 540 nm. Within the calibration range of 0-7.0 mg l(-1) of Cr(VI), the RSD was 0.4% (n=5). The recovery of 0.70 mg l(-1) Cr(VI) added to the waste-water sample was 94.5+/-2.0% (n=5).

Literature study of microwave-assisted digestion using electrothermal atomic absorption spectrometry.

The literature on the use of microwave-assisted digestion procedures for subsequent sample analysis by means of electrothermal atomic absorption spectrometry (ETAAS) is reviewed. The literature survey reveals that this digestion technique has been applied mainly for biological materials. The elements most extensively determined by this method are cadmium and lead followed by copper, chromium, nickel and iron. The microwave digestion conditions, ETAAS furnace programmes and analytical details of the developed methodologies have been carefully revised.

Determination of cadmium by electrothermal atomic absorption spectrometry after microwave-assisted digestion of animal tissues and sewage sludges.

The determination of cadmium in different sample types has been carried out by electrothermal atomization atomic absorption spectrometry with D(2)-background correction using a unpyrocoated graphite tube, after pressurized microwave-assisted digestion. Five chemical modifiers [(NH(4))(2)HPO(4), Pd(NO)(3))(2), Ni(NO(3))(2), thiourea and Triton X-100] have been assayed and nickel nitrate has been found to be most effective for an accurate determination of cadmium in mussel tissue, pig kidney and sewage sludge. The characteristic mass of the method is of the order of 1 pg and the limit of detection is lower than 0.1 ng/ml.

Metal speciation in solid matrices.

The literature on metal ion speciation in solid matrices is reviewed, taking into account its applications in the analysis of soil, sediment, biological materials, foodstuff and other solid samples. The pretreatment methods of various solid materials required for carrying out speciation studies have been highlighted. The basis of the methods of separation of different species from matrices, such as sequential extraction, selective extraction, etc. is discussed. The instrumental techniques used for the characterization of different chemical species in solid matrices have been mentioned. The literature survey reveals the analytical details of the developed methodologies, and these have been examined in terms of the limit of detection, precision and accuracy.

Arsenic content of Spanish cows' milk determined by dry ashing hydride generation atomic absorption spectrometry.

The arsenic content of cows' milk consumed in Spain was determined. A procedure using dry ashing hydride generation atomic absorption spectrometry was developed for the purpose. Experimental conditions for the destruction of organic matter were established and an interference study was carried out. The method developed has a detection limit of 0.1 ng/g, a relative SD of 5%, and a recovery (mean +/- CSI) of 100 +/- 4%. The accuracy of the method was checked by analysis of a certified sample of IAEA milk powder (mean +/- CSI: certified, 4.85 +/- 0.32 ng/g; found, 5.04 +/- 0.81 ng/g). The proposed procedure was used to analyse cows' milk samples. The extremely low arsenic levels found do not present toxicological problems.