Producing Magnetic Nanocomposites from Paper Sludge for the Adsorptive Removal of Pharmaceuticals from Water-A Fractional Factorial Design.

In view of a simple after-use separation, the potentiality of producing magnetic activated carbon (MAC) by intercalation of ferromagnetic metal oxide nanoparticles in the framework of a powder activated carbon (PAC) produced from primary paper sludge was explored in this work. The synthesis conditions to produce cost effective and efficient MACs for the adsorptive removal of pharmaceuticals (amoxicillin, carbamazepine, and diclofenac) from aqueous media were evaluated. For this purpose, a fractional factorial design (FFD) was applied to assess the effect of the most significant variables (Fe3+ to Fe2+ salts ratio, PAC to iron salts ratio, temperature, and pH), on the following responses concerning the resulting MACs: Specific surface area (SBET), saturation magnetization (Ms), and adsorption percentage of amoxicillin, carbamazepine, and diclofenac. The statistical analysis revealed that the PAC to iron salts mass ratio was the main factor affecting the considered responses. A quadratic linear regression model A = f(SBET, Ms) was adjusted to the FFD data, allowing to differentiate four of the eighteen MACs produced. These MACs were distinguished by being easily recovered from aqueous phase using a permanent magnet (Ms of 22-27 emu g-1), and their high SBET (741-795 m2 g-1) were responsible for individual adsorption percentages ranging between 61% and 84% using small MAC doses (35 mg L-1).

Preserve Your Books through the Smell.

The identification of paper composition, pH, early signs of paper degradation, and emitting volatile organic compounds (VOCs) are mandatory for effective preventive conservation of paper/books. Sampling restrictions in the analysis of cultural heritage materials limit the choice of appropriate analytical methods. Solvent-free analytical techniques with nondestructive sampling are needed. Addressing this challenge, an electronic nose based on six-coated piezoelectric quartz crystals was assembled and used to analyze VOCs emitted from books. Careful selection of sensor coatings and cluster analysis allowed us to achieve a clear distinction between cotton/linen rag and wood pulp paper, and among the letter group, the discrimination between papers manufactured from alkaline and acidic stocks. This six-element sensor array was therefore able to replace destructive tests as the ones ordinarily used for paper pH measurements. The same electronic nose was able to separate aged pale-yellow paper, a visible initial sign of paper degradation, from well-preserved still white papers, even when made from the same raw material. One of the used sensors detected furfural, often seen as a marker of cellulose degradation, at lower levels than the detection limit found in the literature with gas chromatography-mass spectrometry, a much more complex bulky and expensive instrument.

Production of highly efficient activated carbons from industrial wastes for the removal of pharmaceuticals from water-A full factorial design.

The wide occurrence of pharmaceuticals in aquatic environments urges the development of cost-effective solutions for their removal from water. In a circular economy context, primary paper mill sludge (PS) was used to produce activated carbon (AC) aiming the adsorptive removal of these contaminants. The use of low-cost precursors for the preparation of ACs capable of competing with commercial ACs continues to be a challenge. A full factorial design of four factors (pyrolysis temperature, residence time, precursor/activating agent ratio, and type of activating agent) at two levels was applied to the production of AC using PS as precursor. The responses analysed were the yield of production, percentage of adsorption for three pharmaceuticals (sulfamethoxazole, carbamazepine, and paroxetine), specific surface area (SBET), and total organic carbon (TOC). Statistical analysis was performed to evaluate influencing factors in the responses and to determine the most favourable production conditions. Four ACs presented very good responses, namely on the adsorption of the pharmaceuticals under study (average adsorption percentage around 78%, which is above that of commercial AC), and SBET between 1389 and 1627 m2 g-1. A desirability analysis pointed out 800 °C for 60 min and a precursor/KOH ratio of 1:1 (w/w) as the optimal production conditions.

Cheeses Made from Raw and Pasteurized Cow's Milk Analysed by an Electronic Nose and an Electronic Tongue.

Cheese prepared from whole milk, raw and pasteurized, were analysed by an electronic nose based on piezoelectric quartz crystals and an electronic tongue based on potentiometric sensors, immediately after their preparation and along ripening (after 7 and 21 days). Whey was also analysed by the potentiometric electronic tongue. Results obtained by the electronic nose and tongue were found to be complementary, with the electronic nose being more sensitive to differences in the milk and the electronic tongue being more sensitive to milk pasteurization. Electronic tongue was able to distinguish cheeses made from raw and pasteurized milk, both analysing the whey or the curd, with correct classification rate of 96% and 84%, respectively. Besides, the electronic nose was more sensitive than the electronic tongue to the ripening process, with large differences between samples after 7 and 21 days, while the electronic tongue was only sensitive to the initial maturation stages, with large difference between freshly prepared cheese and with seven days of maturation.

Adsorptive removal of pharmaceuticals from water by commercial and waste-based carbons.

This work describes the single adsorption of seven pharmaceuticals (carbamazepine, oxazepam, sulfamethoxazole, piroxicam, cetirizine, venlafaxine and paroxetine) from water onto a commercially available activated carbon and a non-activated carbon produced by pyrolysis of primary paper mill sludge. Kinetics and equilibrium adsorption studies were performed using a batch experimental approach. For all pharmaceuticals, both carbons presented fast kinetics (equilibrium times varying from less than 5 min to 120 min), mainly described by a pseudo-second order model. Equilibrium data were appropriately described by the Langmuir and Freundlich isotherm models, the last one giving slightly higher correlation coefficients. The fitted parameters obtained for both models were quite different for the seven pharmaceuticals under study. In order to evaluate the influence of water solubility, log Kow, pKa, polar surface area and number of hydrogen bond acceptors of pharmaceuticals on the adsorption parameters, multiple linear regression analysis was performed. The variability is mainly due to log Kow followed by water solubility, in the case of the waste-based carbon, and due to water solubility in the case of the commercial activated carbon.

An insight into the adsorption and electrochemical processes occurring during the analysis of copper and lead in wines, using an electrochemical quartz crystal nanobalance.

Copper and lead in wine were quantified by anodic stripping voltammetry (ASV), performed onto the gold electrode of a piezoelectric quartz crystal. Both current or mass changes could be used as analytical signals, without a statistical difference in the results (α=0.05). However, the plot of mass vs. potential provided an in depth understanding of the electrochemical processes and allowed studying adsorption phenomena. Copper interaction with fructose is an example of a process which was not possible to ignore by observing the mass change on the gold electrode of the piezoelectric quartz crystal.

An electronic nose based on coated piezoelectric quartz crystals to certify ewes' cheese and to discriminate between cheese varieties.

An electronic nose based on coated piezoelectric quartz crystals was used to distinguish cheese made from ewes' milk, and to distinguish cheese varieties. Two sensors coated with Nafion and Carbowax could certify half the ewes' cheese samples, exclude 32 cheeses made from cow's milk and to classify half of the ewes' cheese samples as possibly authentic. Two other sensors, coated with polyvinylpyrrolidone and triethanolamine clearly distinguished between Flamengo, Brie, Gruyère and Mozzarella cheeses. Brie cheeses were further separated according to their origin, and Mozzarella grated cheese also appeared clearly separated from non-grated Mozzarella.

Detecting spoiled fruit in the house of the future.

An electronic nose based on acoustic wave sensors has been developed to detect spoilt fruit. Different varieties of fruits, edible and rotten, were analysed. Starting from six sensors, the minimum number of sensors capable of discriminating between spoiled and unspoiled fruit was found. The discrimination capability of the sensor array was studied separately for each fruit variety, as well as for the whole set. Mathematical models were built to classify the fruits within a fruit variety, in an objective and clear way. The models were able to distinguish between edible and rotten fruits with 100% success for New Hall oranges, Golden apples, Kiwis and William pears, and with 97.2% of success for the Starking apples. Without forming fruit variety subsets, discrimination between edible and rotten fruit was achieved with 95% success.

Assessment of copper toxicity using an acoustic wave sensor.

A piezoelectric quartz crystal microbalance has been shown to be useful to monitor real time bacterial growth. Monitoring bacterial growth can give an insight into the ecosystem, as it is highly affected by the presence of toxic elements or nutrients. The frequency of an uncoated piezoelectric quartz crystal was monitored while in contact with bacteria, isolated from water sampled from a Portuguese lagoon, growing in two different media: a saline nutrient broth (NM) and the natural water. The sensor was used to evaluate the effect of copper on bacterial growth. Copper concentrations up to 18.8 microg l(-1) showed an increase in bacterial growth in NM, and a decrease beyond 25.0 microg l(-1). Copper added to the natural water had negative effects on bacterial growth beyond 18.8 microg l(-1). Copper concentrations in the natural water from the lagoon were determined using a similar quartz crystal to detect the mass deposited by anodic stripping voltammetry, and was found to be 3.38 +/- 0.09 microg l(-1).

The quantification of sodium in mineral waters using a quartz crystal microbalance.

A sensor for sodium based on a piezoelectric quartz crystal is proposed. The quartz crystal was coated with 5% of bis[(12-crown-4)methyl] dodecylmethylmalonate, 33% of PVC and 62% of NPOE to which KTpClPB in a 22% molar proportion to the ionophore was added. Coating amounts producing a frequency decrease around 18 kHz show optimum linear calibration ranges for the analysis of sodium in commercial mineral waters. Besides sensitivity, coating stability and selectivity of the sensor over other cations were adequate for those analyses. The results obtained analysing commercial mineral waters by the proposed method are not significantly different (alpha=0.05) from the ones obtained by atomic spectrometry.