Environmentally-friendly technology for rapid identification and quantification of emerging pollutants from wastewater using infrared spectroscopy.

The monitoring of emerging pollutants in wastewaters is nowadays an issue of special concern, with the classical quantification methods being time and reagent consuming. In this sense, a FTIR transmission spectroscopy based chemometric methodology was developed for the determination of eight of these pollutants. A total of 456 samples were, therefore, obtained, from an activated sludge wastewater treatment process spiked with the studied pollutants, and analysed in the range of 200 cm-1 to 14,000 cm-1. Then, a k-nearest neighbour (kNN) analysis aiming at identifying each sample pollutant was employed. Next, partial least squares (PLS) and ordinary least squares (OLS) modelling approaches were employed in order to obtain suitable prediction models. This procedure resulted in good prediction abilities regarding the estimation of atrazine, desloratadine, paracetamol, ß-estradiol, ibuprofen, carbamazepine, sulfamethoxazole and ethynylestradiol concentrations in wastewaters. These promising results suggest this technology as a fast, eco-friendly and reagent free alternative methodology for the quantification of emerging pollutants in wastewaters.

Quantification of pharmaceutical compounds in wastewater samples by near infrared spectroscopy (NIR).

The quantification of pollutants, as pharmaceuticals, in wastewater is an issue of special concern. Usually, typical methods to quantify these products are time and reagent consuming. This paper describes the development and validation of a Fourier transform near-infrared (FT-NIR) spectroscopy methodology for the quantification of pharmaceuticals in wastewaters. For this purpose, 276 samples obtained from an activated sludge wastewater treatment process were analysed in the range of 200 cm-1 to 14,000 cm-1, and further treated by chemometric techniques to develop and validate the quantification models. The obtained results were found adequate for the prediction of ibuprofen, sulfamethoxazole, 17ß-estradiol and carbamazepine with coefficients of determination (R2) around 0.95 and residual prediction deviation (RPD) values above four, for the overall (training and validation) data points. These results are very promising and confirm that this technology can be seen as an alternative for the quantification of pharmaceuticals in wastewater.

New PLS analysis approach to wine volatile compounds characterization by near infrared spectroscopy (NIR).

This work aims to explore the potential of near infrared (NIR) spectroscopy to quantify volatile compounds in Vinho Verde wines, commonly determined by gas chromatography. For this purpose, 105 Vinho Verde wine samples were analyzed using Fourier transform near infrared (FT-NIR) transmission spectroscopy in the range of 5435 cm-1 to 6357 cm-1. Boxplot and principal components analysis (PCA) were performed for clusters identification and outliers removal. A partial least square (PLS) regression was then applied to develop the calibration models, by a new iterative approach. The predictive ability of the models was confirmed by an external validation procedure with an independent sample set. The obtained results could be considered as quite good with coefficients of determination (R2) varying from 0.94 to 0.97. The current methodology, using NIR spectroscopy and chemometrics, can be seen as a promising rapid tool to determine volatile compounds in Vinho Verde wines.

Treatment of chromium(VI) solutions in a pilot-scale bioreactor through a biofilm of Arthrobacter viscosus supported on GAC.

The aim of this work is to evaluate the applicability of a biofilm to the removal of chromium in solution, at a pilot scale. The effect of the initial concentration of metal on the biosorption behavior of an Arthrobacter viscosus biofilm supported on granular activated carbon, in batch and column essays was also analyzed. Six isotherm equations have been tested in the present study. The best fit was obtained with the Freundlich model. It was observed that as the initial chromium concentration increases, the uptake increases too, but the removal percentage decreases, with values between 95.20% (C(0)=5mg/l) and 38.28% (C(0)=1000 mg/l). The batch adsorption studies were used to develop a pilot bioreactor able to remove chromium from aqueous solutions. Data obtained in a pilot-scale reactor showed an average removal percentage of 99.9%, during the first 30 days, for the initial concentration of 10mg/l and an average removal percentage of 72%, for the same period and for the initial concentration of 100mg/l. Uptake values of 11.35 mg/g and 14.55 mg/g were obtained, respectively, for the initial concentration of 10 and 100mg/l. The results obtained are very promising and encourage the utilization of this biofilm in environmental applications.

Biosorption of Cr(VI) by three different bacterial species supported on granular activated carbon: a comparative study.

The ability of three different bacterial species supported on granular activated carbon (GAC) to remove hexavalent chromium from low concentration liquid solutions was investigated, in batch and column studies. The microorganisms tested were Cr(VI) reducing types: Streptococcus equisimilis (CECT 926), Bacillus coagulans (CECT 12) and Escherichia coli (CECT 515). The results showed metal uptake values of 5.82, 5.35 and 4.12 mg/g(bios.), respectively, for S. equisimilis, B. coagulans and E. coli, for an initial metal concentration of 100 mg/l. In the same order and for the initial concentration of 50 mg/l, metal uptake values were 2.33, 1.98 and 3.60 mg/g(bios.). Finally, for the initial metal concentration of 10 mg/l, those values were, respectively, 0.66, 1.51 and 1.12 mg/g(bios.). Studies made with an industrial effluent, with the aim of testing these biofilms in a real situation, showed values of Cr uptake of 0.083, 0.090 and 0.110 mg/g(bios.), respectively, for S. equisimilis, B. coagulans and E. coli, for an initial concentration of 4.2 mg/l of total Cr. The quantification of polysaccharides, playing a key role in the whole process, was made and it was concluded that the production of polysaccharides is higher for B. coagulans followed by S. equisimilis and E. coli (9.19, 7.24 and 4.77 mg/g(bios.)). The batch studies data were described using the Freundlich, Langmuir, Redlich-Peterson, Dubinin-Radushkevich, Sips and Toth model isotherms. The best fit was obtained with Sips and Toth model isotherms, respectively, for the S. equisimilis and for the B. coagulans biofilms. For the E. coli biofilm the Freundlich, Redlich-Peterson, Sips and Toth models fitted very well to the experimental data. The Adams-Bohart, Wolborska and Yoon and Nelson models were applied to column studies data. Those models were found suitable for describing the dynamic behaviour of the columns with respect to the inlet chromium concentration. Obtained results showed that the biofilms tested are very promising for the removal of Cr(VI) in diluted industrial wastewater. Despite differences in the cell wall structure and composition, the three bacteria exhibit comparable sorption affinities towards chromium, in the open systems studies. The Gram-positive bacteria tested (B. coagulans and S. equisimilis) presented best metal removal percentages in batch studies.