In situ formation of CuxO/ZnO photocatalysts for efficient simultaneous oxidation of As (III) and adsorption of As (V): Effect of Cu loading.

The introduction of Cu ions onto ZnO leads to alterations in the electrical, optical, and magnetic characteristics of ZnO. These transformations, in turn, result in heightened photocatalytic activity and enhanced stability when employed in the degradation of both organic and inorganic pollutants. Here, a novel photocatalytic-adsorbent system is developed using zinc oxide (ZnO) nanostructures modified with Cu (II) ions in an aqueous solution containing 40 mg/L of As (III). The system utilizes UV-A light (365 nm) as the irradiation source, and the weight percentage of Cu (II) in the composite varies from 0 to 20%. The experimental results reveal significant adsorption of As (III), ranging from 20 to 50%, depending on the solution's Cu (II) content. Remarkably, the ZnO10%Cu composite exhibits the highest photocatalytic activity, achieving 40% adsorption and complete oxidation of As (III) within 25 min of irradiation. Characterization of the composite after the photocatalytic treatment reveals the effective adsorption of As (V) within its structure. Furthermore, no traces of Cu (II) ions are detected in the solution after the reaction, indicating their successful adsorption onto the ZnO surface as Cu (I) and Cu (II) ions. This research marks a significant advancement in harnessing innovative materials for efficient arsenic removal, offering promising insights into the development of novel photocatalytic-adsorbent systems.

Monitorization of polyamide microplastics weathering using attenuated total reflectance and microreflectance infrared spectrometry.

The EU goal to reduce marine plastic litter by ca. 30% by 2020 stressed the need to deploy analytical methods to ascertain the polymeric nature of a residue. Furthermore, as plastics age under natural conditions and usual databases do not include their weathered spectra, (micro)plastics in environmental samples may be unidentified. In this paper, polyamide (nylon) microplastics weathering was monitored because of its ubiquity in household commodities, clothes, fishery items and industry, whose residues end up frequently in the environment. Infrared spectra (ATR and microreflectance) and Scanning Electron Microscopy (SEM) images were collected periodically while exposing nylon to controlled weathering. It was seen that ATR was more sensitive than microreflectance to monitor the structural evolution of polyamide and that the spectra and the surface of weathered microplastics showed remarkable differences with the pristine material, which stresses the need for considering its evolution when identifying microplastics in environmental studies. The evolution of six band ratios related to the chemical evolution of this polymer are presented. SEM images revealed the formation of secondary microplastics at the most advanced weathering stages of polyamide.

Determination of cadmium in sediments by diluted HCI extraction and isotope dilution ICP-MS.

Isotope dilution ICP-MS is proposed to measure the mass fraction of Cd extracted by diluted HCl in marine sediments, using a fast and simple extraction procedure based on ultrasonic probe agitation. The 111Cd isotope was added before the extraction to achieve isotope equilibration with native Cd solubilized from the sample. The parameters affecting trueness and precision of isotope ratio measurements were evaluated carefully and subsequently corrected in order to minimize errors; they were: detector dead time, spectral interferences, mass discrimination factor and optimum sample/spike ratio. The mass fraction of Cd extracted was compared with the sum of the certified contents of the three steps of the sequential extraction procedure of the Standards, Measurements and Testing Programme (SM&T) analysing the BCR 701 sediment to validate the method. The certified and measured values agreed, giving a measured / certified mass fraction ratio of 1.05. Further, the extraction procedure itself was studied by adding the enriched isotope after the extraction step, which allowed verifying that analyte losses occurred during this process. Two additional reference sediments with certified total cadmium contents were also analysed. The method provided very good precision (0.9%, RSD) and a low detection limit, 1.8 ng g-1. The procedural uncertainty budget was estimated following the EURACHEM Guide by means of the 'GUM Workbench' software, obtaining a relative expanded uncertainty of 1.5%. The procedure was applied to determine the bioaccessible mass fraction of Cd in sediments from two environmentally and economically important areas of Galicia (rias of Arousa and Vigo, NW of Spain).

Chemometric tools to evaluate the spatial distribution of trace metals in surface sediments of two Spanish rías.

A suite of relevant trace metals (Hg, Pb, Cd, Cu, Zn and Ni) was measured in surface sediment samples to assess the environmental situation of the largest two Atlantic Spanish 'rías' (a form of estuaries, ría of Pontevedra, ROP, and ría of Vigo, ROV). The level of contamination originated by these metals was assessed against international guidelines, the threshold effect, ERL, and the midrange effect, ERM. Six unsupervised and supervised multivariate chemometric techniques were applied to model each ría, compare them and select those metals that characterize the samples. This is first time that such a study is performed for these two important seafood-producing areas. Maximum concentrations at ROP occurred in the vicinities of an inner island, where Cu, Zn, Ni and Pb presented concentrations over the ERL and Hg over the ERM. Highest concentrations of metals in ROV were observed in the proximities of Vigo shipyards and port, except for Pb, with peak values in San Simon Bay. ERL limits were exceeded in the inner part of this ría for Cu, Zn and Hg and in a wider area for Pb and Ni. Levels for Pb went beyond the ERM boundary in the axial part of San Simon Bay. In general, the distribution of the metals was more homogeneous in ría of Pontevedra than in ría of Vigo (where three morphological zones were characterized). Both rías could be differentiated using only two metals: Ni and Hg, as deduced from the multivariate techniques.

Comparison of the 2000 and 2005 spatial distributions of heavy metals in wild mussels from the North-Atlantic Spanish coast.

Spatial distributions of Cd, Cu, Hg, Pb and Zn in Mytilus galloprovincialis in 41 sampling sites in the North-Atlantic Spanish coast were monitored in 2000 and 2005 to assess the coastal environmental pollution. A pool of mussel soft tissue was prepared using 50 or more individuals representing the available size range. Samples were grounded, homogenised and quantified by atomic absorption spectrometry. Quality of the chemical analyses was assessed by participation in periodic interlaboratory exercises. Univariate and multivariate statistical studies, Principal Components Analysis and Procrustes rotation (a technique intended to compare several data spaces) were carried out. Some decreasing trends were observed for the concentrations throughout the 2000-2005 period, mainly for Hg and Pb. In general, the Northern area showed higher median concentrations (e.g., 3.79 and 4.28 mg Pb/kg dry weight, and 0.160 and 0.191 mg Hg/kg dry weight, for 2000 and 2005, respectively) than the Atlantic ones (e.g., 1.47 and 1.44 mg Pb/kg dry weight, and 0.097 and 0.084 mgHg/kg dry weight, for 2000 and 2005, respectively). Nevertheless, some Atlantic sampling points, located far from human inputs (cities, industries, rivers, etc.) exhibited high concentrations of Cd, which was attributed to the influence of the natural upwelling processes which occur annually in that geographical region.

The real-time polymerase chain reaction.

The scientific, medical, and diagnostic communities have been presented the most powerful tool for quantitative nucleic acids analysis: real-time PCR [Bustin, S.A., 2004. A-Z of Quantitative PCR. IUL Press, San Diego, CA]. This new technique is a refinement of the original Polymerase Chain Reaction (PCR) developed by Kary Mullis and coworkers in the mid 80:ies [Saiki, R.K., et al., 1985. Enzymatic amplification of beta-globin genomic sequences and restriction site analysis for diagnosis of sickle cell anemia, Science 230, 1350], for which Kary Mullis was awarded the 1993 year's Nobel prize in Chemistry. By PCR essentially any nucleic acid sequence present in a complex sample can be amplified in a cyclic process to generate a large number of identical copies that can readily be analyzed. This made it possible, for example, to manipulate DNA for cloning purposes, genetic engineering, and sequencing. But as an analytical technique the original PCR method had some serious limitations. By first amplifying the DNA sequence and then analyzing the product, quantification was exceedingly difficult since the PCR gave rise to essentially the same amount of product independently of the initial amount of DNA template molecules that were present. This limitation was resolved in 1992 by the development of real-time PCR by Higuchi et al. [Higuchi, R., Dollinger, G., Walsh, P.S., Griffith, R., 1992. Simultaneous amplification and detection of specific DNA-sequences. Bio-Technology 10(4), 413-417]. In real-time PCR the amount of product formed is monitored during the course of the reaction by monitoring the fluorescence of dyes or probes introduced into the reaction that is proportional to the amount of product formed, and the number of amplification cycles required to obtain a particular amount of DNA molecules is registered. Assuming a certain amplification efficiency, which typically is close to a doubling of the number of molecules per amplification cycle, it is possible to calculate the number of DNA molecules of the amplified sequence that were initially present in the sample. With the highly efficient detection chemistries, sensitive instrumentation, and optimized assays that are available today the number of DNA molecules of a particular sequence in a complex sample can be determined with unprecedented accuracy and sensitivity sufficient to detect a single molecule. Typical uses of real-time PCR include pathogen detection, gene expression analysis, single nucleotide polymorphism (SNP) analysis, analysis of chromosome aberrations, and most recently also protein detection by real-time immuno PCR.