Validation and uncertainty estimation of analytical method for quantification of phytochelatins in aquatic plants by UPLC-MS.

Phytochelatins (PCs) are peptides that play an important role in homeostasis and detoxification of heavy metal in plants. Furthermore, they have been proposed as earlier potential biomarkers of aquatic pollution by heavy metals. Nowadays, several researchers have reported on current methods for quantification of glutathione (GSH) and the PCs (phytochelatin 2, phytochelatin 3, phytochelatin 4) quantification in plants. However, no method has reported the uncertainty of the measurement, which helps to improve the accuracy and quality assurance in the PC quantification. In this work, a new methodology using ultra-high-performance liquid chromatography coupled to mass spectrometry (UPLC-MS) to measure with high precision and accuracy the PCs in aquatic plants, was validated. Selectivity, linearity, limit of detection, limit of quantification, precision, trueness and uncertainty estimation were examined as parts of the method validation. The described method shows excellent linearity in different ranges for all analytes with coefficients of determination higher than 0.99. The relative standard deviation for intra-day precision was <3% and for inter-day <10%. All LOD and LOQ analytes ranged from 0.02 to 0.08 µg ml-1, and from 0.03 to 0.09 µg ml-1, respectively. The recoveries varied from 61% to 89%. In order to obtain an interval of results with the highest confidence levels, the uncertainty associated with the measurements was evaluated. The calibration curve (>50%) and recovery (19-44%) were the most important contributors to the total uncertainty. The proposed method was applied to quantify GSH and PCs in the aquatic plants Lemna gibba L., Myriophyllum heterophyllum Michx., Arenaria paludicola and Hydrocotyle ranunculoides L. fil., showing statistical differences in the mass fraction of the analytes.

Removal of phenanthrene in aqueous solution containing photon competitors by TiO2-C-Ag film supported on fiberglass.

Surface interactions with pollutants and photons are key factors that affect the applications of TiO2 in environmental remediation. In this study, the solubilizing agents dimethylsulfoxide and polyoxyethylene sorbitan monooleate, which act as photon competitors, had no effect on the photocatalytic activity of TiO2-C-Ag film in phenanthrene (PHE) removal. Fiberglass with TiO2-C-Ag coating removed 91.1 ± 5.2 and 99.7 ± 0.4% of PHE in treatments using UVA (365-465 nm) and UVC (254 nm) irradiation, respectively. The use of fiberglass as a support increased the superficial area, thus allowing PHE sorption. C and Ag, which are electrically active impurities in TiO2, enhanced its photocatalytic activity and thus the attraction of the pollutant to its surface. The use of high-frequency UV light (UVC) decreased the amount of carbon species deposited on the TiO2CAg film surface. X-ray photoelectron spectroscopy of the TiO2-C-Ag film revealed extensive oxidation of the carbon deposited on the film under UVC light and loss of electrons from Ag clusters by conversion of Ag0 to Ag3+.

Assessment of spatial variability of heavy metals in Metropolitan Zone of Toluca Valley, Mexico, using the biomonitoring technique in mosses and TXRF analysis.

This study is aimed at assessing atmospheric deposition of heavy metals using the epiphytic moss genera Fabronia ciliaris collected from six urban sites in the Metropolitan Zone of the Toluca Valley in Mexico. The concentrations of K, Ca, Ti, V, Cr, Mn, Fe, Ni, Cu, Zn, Rb, Sr, and Pb were determined by total reflection X-ray fluorescence technique. Results show that the average metal concentration decrease in the following order: Fe (8207 mg/Kg) > Ca (7315 mg/Kg) > K (3842 mg/Kg) > Ti (387 mg/Kg) > Mn, Zn (191 mg/Kg) > Sr (71 mg/Kg) > Pb (59 mg/Kg) > Cu, V (32 mg/Kg) > Cr (24 mg/Kg) > Rb (13 mg/Kg) > Ni (10 mg/Kg). Enrichment factors show a high enrichment for Cr, Cu, Zn, and Pb which provides an evidence of anthropogenic impact in the industrial and urban areas, mainly due to the intense vehicular traffic and the fossil fuel combustion. Monitoring techniques in mosses have proved to be a powerful tool for determining the deposition of heavy metals coming from diverse point sources of pollution.

Determination of distributions of Cd, Cu, and Pb concentrations in sediments of a Mexican reservoir to infer their environmental risk.

The José Antonio Alzate Dam in the State of Mexico, Mexico, receives wastewaters from domestic, industrial, and agricultural activities through the Lerma River. Chemical and physicochemical characteristics of the water were determined. Sediment has been studied in order to define the importance of its influence on the reservoir's state as a whole. The quantification of the metals, Cd, Cu, and Pb in total forms and the geochemical distribution and the chemical mobility of these metals in sediment have been established using a chemical sequential extraction scheme. The three metals showed a common characteristic, being more abundant in fraction F6 (residual), but the other fractions of the geochemical distribution were variable depending on the metal. First, the contamination level was evaluated with the results of the total metals, using the criteria of EPA, Thomas and Murdoch, and the Ontario Ministry of Environment for sediment in water bodies. Subsequently, the risk was assessed using the same criteria but considering the results of sequential extractions, where the geochemical distribution of each metal allowed a better understanding of metal portions with more influence on the risk, in which Cu and Pb presented low risk, but not Cd.

Calculation of the ecological risk index in the José Antonio Alzate Dam, State of Mexico, Mexico.

Due to the problem of contamination in the Jose Antonio Alzate dam, located in the State of Mexico, Mexico, the partition coefficient, the contamination degree, and the ecological risk index of nine metals were calculated in order to establish the water quality in different areas of the Alzate dam. The sampling sites were selected according to the river flow into the dam, via three sampling programs, the physical-chemical parameters were measured in situ, and the samples were collected to measure metals in the dissolved phase and also as suspended particulate matter. Thomann's model was used to calculate the partition coefficient. Håkanson's methodology was used to determine the degree of contamination and the ecological risk index. Finally, the water quality criteria for the dissolved metals were calculated. The results for suspended particulate matter suggest a moderate risk of metal contamination in the dam. Copper and lead in dissolved form exceeded the values of water quality criteria.