Use of Uncertainty Calculation Software as a Didactic Tool to Improve the Knowledge of Chemistry Students in Analytical Method Validation.

Calculating analytical uncertainties as a part of method validation is a relevant aspect of field and laboratory practices in instrumental analytical chemistry subjects, which usually require complex algorithms. This work describes the development and didactic use of an automatic and straightforward informatics tool, implemented in an Excel macro, for calculating and interpreting the uncertainty of an analytical method against a reference method on field measurements. The software was initially developed for field testing of low-cost air quality monitoring analytical methods against reference methods, and the present work shows its adaptation to a didactic environment. The uncertainty calculation software was implemented through an Excel macro based on Visual Basic as a graphical user interface. It finds a best-fit line that describes the relation between concentrations determined by the candidate and reference methods. The software generates the analytical validation results (slope and intercept with their respective confidence limits, and expanded uncertainty of a concentration determined by the candidate method), hiding the intermediate functions and calculations. The Excel interface eases uncertainty calculations for undergraduate students, although the background mathematics can be quickly unveiled to students for didactic purposes. This tool has been applied to a laboratory exercise focused on validating experimental results obtained in the measurement of ozone levels in ambient air by passive sampling and spectrophotometric detection. The uncertainty calculation software has proved valuable by providing the student a resource to check the analytical quality of the data generated in the laboratory, while assimilating the fundamentals behind the calculations.

Wearable system for outdoor air quality monitoring in a WSN with cloud computing: Design, validation and deployment.

Breathing poor-quality air is a global threat at the same level as unhealthy diets or tobacco smoking, so the availability of affordable instrument for the measurement of air pollutant levels is highly relevant for human and environmental protection. We developed an air quality monitoring platform that comprises a wearable device embedding low-cost metal oxide semiconductor (MOS) gas sensors, a PM sensor, and a smartphone for collecting the data using Bluetooth Low Energy (BLE) communication. Our own developed app displays information about the air surrounding the user and sends the gathered geolocalized data to a cloud, where the users can map the air quality levels measured in the network. The resulting device is small-sized, light-weighted, compact, and belt-worn, with a user-friendly interface and a low cost. The data collected by the sensor array are validated in two experimental setups, first in laboratory-controlled conditions and then against referential pollutant concentrations measured by standard instruments in an outdoor environment. The performance of our air quality platform was tested in a field testing campaign in Barcelona with six moving devices acting as wireless sensor nodes. Devices were trained by means of machine learning algorithms to differentiate between air quality index (AQI) referential concentration values (97% success in the laboratory, 82.3% success in the field). Humidity correction was applied to all data.

A Novel Bike-Mounted Sensing Device with Cloud Connectivity for Dynamic Air-Quality Monitoring by Urban Cyclists.

We present a device based on low-cost electrochemical and optical sensors, designed to be attached to bicycle handlebars, with the aim of monitoring the air quality in urban environments. The system has three electrochemical sensors for measuring NO2 and O3 and an optical particle-matter (PM) sensor for PM2.5 and PM10 concentrations. The electronic instrumentation was home-developed for this application. To ensure a constant air flow, the input fan of the particle sensor is used as an air supply pump to the rest of the sensors. Eight identical devices were built; two were collocated in parallel with a reference urban-air-quality-monitoring station and calibrated using a neural network (R2 > 0.83). Several bicycle routes were carried out throughout the city of Badajoz (Spain) to allow the device to be tested in real field conditions. An air-quality index was calculated to facilitate the user's understanding. The results show that this index provides data on the spatiotemporal variability of pollutants between the central and peripheral areas, including changes between weekdays and weekends and between different times of the day, thus providing valuable information for citizens through a dedicated cloud-based data platform.

Screen-Printed Gold Electrodes as Passive Samplers and Voltammetric Platforms for the Determination of Gaseous Elemental Mercury.

We present a methodology for the determination of gaseous elemental mercury (GEM). It is based on passive sampling of Hg on screen-printed gold electrodes (SPGEs), followed by the measurement of amalgamated mercury by square wave anodic stripping voltammetry. We have explored in detail the behavior of the SPGE electrode surface during the sampling process (by time-of-flight secondary ion mass spectrometry), the stability of the voltammetric signals, and the inter-electrode reproducibility, and obtained acceptable results. Adsorption of mercury onto the SPGE follows a nearly linear behavior until the sorbent becomes saturated (equilibrium phase) for different mercury concentrations, allowing to select a sampling time of 30 min for calibration. The theoretical behavior of the sampling system was modeled, considering the changes in the diffusive path length between the porous diffusive barrier and the adsorbed surface, L. Finally, we have tested two GEM calibration protocols. The first one is based on the measurement of the mercury stripping peak area, AHg, and the second one is based on the measurement of the mass of mercury, mHg, by standard additions. We found good correlation coefficients between the GEM concentration for both AHg (R2 = 0.9591) and mHg (R2 = 9615) in the range of 5.82 to 59.29 ng dm-3 GEM. Detection limits were 5.32 and 5.22 ng dm-3 for AHg and mHg, respectively. Our results open a new line of electroanalytical strategies for the determination of GEM in atmospheric samples.

Optimization and validation test of a sonoreactor-assisted methodology for fast and miniaturized extraction of trace elements from soils.

We have proven the overall applicability of the novel sonoreactor VialTweeter as a tool for a fast, miniaturized and economical extraction of trace elements, namely Cu, Zn, As, Cd, Pb, from soil samples, followed by ICP-MS. The proposed analytical approach applicable in the context of environmental monitoring of elemental soil pollutants, since the selected analytes are relevant pollutants whose presence in soils produces significant effects on their quality affecting animals, plants and humans. The optimum conditions for the extraction of trace metals assisted by the sonoreactor, selected by a Box-Behnken (BBD) experiment design along combined with a response surface methodology were 93% sonication amplitude, 450 s sonication time, 80% HNO3 and a solvent/sample ratio of 0.18 mL/mg. The proposed sonoreactor-assisted extraction methodology provides several advantages of respect to the standard acid digestion taken as comparison term for validation, including a shorter pretreatment time and use of less sample and reagents amounts. However, mixed validation results against the standard acid digestion (taken as a model providing accurate results) were obtained depending on the analyte, with the best results in the case of cadmium that could be measured after US extraction without systematic error respect to the standard acid digestion. Copper and lead can be determined by the proposed US extraction plus ICP-MS only after applying a correction factor based on the slope of the correlation with the standard acid digestion. US treatment for As determination can be only useable by applying a constant correction factor based on the intercept of the correlation line, whereas Zn determination requires a correction based both in the slope and intercept of the correlation line.

Radon and thoron exhalation rate, emanation factor and radioactivity risks of building materials of the Iberian Peninsula.

Radon (222Rn) and thoron (220Rn) are radioactive gases emanating from geological materials. Inhalation of these gases is closely related to an increase in the probability of lung cancer if the levels are high. The majority of studies focus on radon, and the thoron is normally ignored because of its short half-life (55.6 s). However, thoron decay products can also cause a significant increase in dose. In buildings with high radon levels, the main mechanism for entry of radon is pressure-driven flow of soil gas through cracks in the floor. Both radon and thoron can also be released from building materials to the indoor atmosphere. In this work, we study the radon and thoron exhalation and emanation properties of an extended variety of common building materials manufactured in the Iberian Peninsula (Portugal and Spain) but exported and used in all countries of the world. Radon and thoron emission from samples collected in the closed chamber was measured by an active method that uses a continuous radon/thoron monitor. The correlations between exhalation rates of these gases and their parent nuclide exhalation (radium/thorium) concentrations were examined. Finally, indoor radon and thoron and the annual effective dose were calculated from radon/thoron concentrations in the closed chamber. Zircon is the material with the highest concentration values of 226Ra and 232Th and the exhalation and emanation rates. Also in the case of zircon and some granites, the annual effective dose was higher than the annual exposure limit for the general public of 1 mSv y-1, recommended by the European regulations.

Estimation of PM10 Levels and Sources in Air Quality Networks by Digital Analysis of Smartphone Camera Images Taken from Samples Deposited on Filters.

This paper explores the performance of smartphone cameras as low-cost and easily accessible tools to provide information about the levels and origin of particulate matter (PM) in ambient air. We tested the concept by digital analysis of the images of daily PM10 (particles with diameters 10 µm and smaller) samples captured on glass fibre filters by high-volume aerosol samplers at urban and rural locations belonging to the air quality monitoring network of Extremadura (Spain) for one year. The images were taken by placing the filters inside a box designed to maintain controlled and reproducible light conditions. Digital image analysis was carried out by a mobile colour-sensing application using red, green, blue/hue, saturation, value/hue, saturation, luminance (RGB/HSV/HSL) parameters, that were processed through statistical procedures, directly or transformed to greyscale. The results of the study show that digital image analysis of the filters can roughly estimate the concentration of PM10 within an air quality network, based on a significant linear correlation between the concentration of PM10 measured by an official gravimetric method and the colour parameters of the filters' images, with better results in the case of the saturation parameter (SHSV). The methodology based on digital analysis can discriminate urban and rural sampling locations affected by different local particle-emitting sources and is also able to identify the presence of remote sources such as Saharan dust outbreaks in both urban and rural locations. The proposed methodology can be considered as a useful complement to the aerosol sampling equipment of air quality network field units for a quick estimation of PM10 in the ambient air, through a simple, accessible and low-cost procedure, with further miniaturization potential.

Nafion-Protected Sputtered-Bismuth Screen-Printed Electrode for On-site Voltammetric Measurements of Cd(II) and Pb(II) in Natural Water Samples.

In this work, we explore the protection with Nafion of commercial sputtered-bismuth screen-printed electrodes (BiSPSPEs), to improve its ability for on-site determination of Cd(II) and Pb(II) ions in ambient water samples. The modified screen-printed platform was coupled with a miniaturized cell, in combination with a battery-operated stirring system and a portable potentiostat operated by a laptop for decentralized electrochemical measurements using Square-Wave Anodic Stripping Voltammetry (SWASV). We also describe a detailed electrode surface characterization by microscopy and surface analysis techniques, before and after the modification with Nafion, to get insight about modification effect on signal size and stability. Optimization of the chemical composition of the medium including the optimization of pH, and instrumental parameters, resulted in a method with detection limits in the low ng/mL range (3.62 and 3.83 ng·mL-1 for Cd and Pb respectively). Our results show an improvement of the sensitivity and stability for Nafion-protected BiSPSPEs in pH = 4.4 medium, and similar or lower detection limits than comparable methods on commercial BiSPSPEs. The values obtained for Pb(II) and Cd(II) in natural water samples agreed well with those obtained by the much more costly Inductively Coupled Plasma Mass Spectrometry, ICP-MS, technique as a reference method (recoveries from 75% to 111%).

Fast and direct amperometric analysis of polyphenols in beers using tyrosinase-modified screen-printed gold nanoparticles biosensors.

In this work it is explored a real applicability of miniaturised and portable biosensing technology for the estimation of total phenolic content in 15 different commercial beers by applying direct amperometry. Gold nanoparticles screen-printed electrodes were thoroughly modified with tyrosinase (Tyr-AuNPS-SPCEs), which was immobilised on the surface by crosslinking with glutaraldehyde. All chemical and instrumental variables involved in the electrochemical method were optimised to develop a reliable and powerful tool to estimate rapidly the content of phenolic compounds in complex beer samples. Catechol, phenol, caffeic acid and tyrosol were analysed individually using the proposed methodology and good analytical and kinetic performances were obtained. Total phenolic content in tested beers (high fermented, low fermented and non-alcoholic) were expressed as mg L-1 of tyrosol, which is one of the major phenolic compound reported in beer. Moreover, the developed amperometric methodology was successfully benchmarked against standardised Folin-Ciocalteau spectrophotometric method with a good Pearson correlation (r = 0.821, p < 0.01). Hierarchical Cluster Analysis (HCA) was also applied on electrochemical results and a good capability to group tested beers based on their tyrosol concentration was demonstrated.

Long-term assessment of ecological risk from deposition of elemental pollutants in the vicinity of the industrial area of Puchuncaví-Ventanas, central Chile.

The present work investigates soil pollution by elemental contaminants and compares ecological risk indexes related to industrial activities for the case study of Puchuncaví-Ventanas: a relevant industrial zone located in central Chile. Selected elements (As, Pb, Cd, Ni, Hg, V, Mn, Zn, Sr, Sb, Cr, Co, Cu, K, and Ba) were analyzed during a long-term period (yearly sampling campaigns during 2007-2011), at 5 sampling stations representing different degrees of impact. PCA and cluster analysis allowed identifying a copper smelter and a coal-fired power plant complex as major pollution sources. Geoaccumulation index (I geo), enrichment factor (EF), contamination factor (Cf), contamination degree (C deg), and integrated pollution index (IPI) are critically discussed for quantitative ecological risk assessment. I geo, EF and Cf indexes are producing comparable environmental information, showing moderate to high pollution risks in the area that demands further monitoring and adoption of prevention and remediation measures. CAPSULE: Long term assessment of elemental pollution around an industrial area. New insight on ecological risk indexes for trace element pollution in soils, by critical comparison among them.