Use of the dummy approach for the synthesis of ion imprinted polymers with Ni(II) or Zn(II) as template ion for the solid-phase extraction of Cu(II).

There is a strong interest in monitoring copper in environmental waters, but its direct analysis suffers from strong matrix interferences. This is why, a sample pretreatment based on solid-phase extraction (SPE) is often used but conventional sorbents usually lack specificity. It is overcome with ion-imprinted polymers (IIPs). This work evaluates for the first time the use of the dummy approach for the synthesis of Cu(II)-targeting IIPs. Two analog ions Ni(II) and Zn(II) were tested as templates and the resulting IIPs were packed in SPE cartridges. The SPE procedure was designed by optimizing a washing step following the sample percolation, to eliminate the interfering ions retained on the IIP by non-specific interactions. To optimize the washing step, solutions at different pH or containing tris(hydroxymethyl)aminomethane as a complexing agent at different concentrations were tested and combined. Zn-IIP appeared more promising than Ni-IIP, showing excellent specificity and a high selectivity. Its retention capacity was determined to be 100 µg/g, and different isotherm models were evaluated to fit with the adsorption data. Finally, applications to mineral and sea waters were successfully completed and led to high and repeatable extraction recoveries for Cu(II) (88 ± 1% and 83 ± 3%, respectively).

Development of ion-imprinted polymers for the selective extraction of Cu(II) ions in environmental waters.

Several ion-imprinted polymers (IIPs) were synthesized via bulk polymerization with Cu(II) as template ion, methacrylic acid as functional monomer, ethylene glycol dimethacrylate as crosslinking agent, and azobisisobutyronitrile as initiator in acetonitrile or methanol as porogen solvent. Non-imprinted polymers (NIPs) were similarly synthesized but without Cu(II). After grounding and sieving, the template ions were removed from IIPs particles through several cycles of elimination in 3 M HCl. All NIPs were equally subjected to this acid treatment with the exception of one NIP, called unwashed NIP. The resulting IIP/NIP particles were packed in solid phase extraction (SPE) cartridges for characterization. The SPE protocol was designed by optimizing a washing step following the sample percolation to eliminate potential interfering ions prior to the elution of Cu(II), all fractions analyzed by inductively coupled plasma mass spectrometry. The best IIP showed a high specificity (recovery of Cu(II) vs. interfering ions) and a good selectivity (retention on IIP vs. NIP). Its adsorption capacity was determined to be 63 µg g-1. Then, a volume of 50 mL was percolated with 30 mg of IIP, thus giving rise to an enrichment factor of 24. Finally, applications to real samples (mineral and sea waters) were successfully performed. In addition, Brunauer-Emmett-Teller analyses showed that the surface area of the washed NIP was almost double that of the unwashed one (140.70 vs. 74.49 m2 g-1), demonstrating for the first time that the post-treatment of a NIP after its synthesis may have a significant impact on its porous structure, and thus need to be more precisely detailed by authors in the future papers.

Surface Functionalization with Polymer Membrane or SEIRA Interface to Improve the Sensitivity of Chalcogenide-Based Infrared Sensors Dedicated to the Detection of Organic Molecules.

Priority substances likely to pollute water can be characterized by mid-infrared spectroscopy based on their specific absorption spectral signature. In this work, the detection of volatile aromatic molecules in the aqueous phase by evanescent-wave spectroscopy has been optimized to improve the detection efficiency of future in situ optical sensors based on chalcogenide waveguides. To this end, a hydrophobic polymer was deposited on the surface of a zinc selenide prism using drop and spin-coating methods. To ensure that the water absorption bands will be properly attenuated for the selenide waveguides, two polymers were selected and compared: polyisobutylene and ethylene/propylene copolymer coating. The system was tested with benzene, toluene, and ortho-, meta-, and para-xylenes at concentrations ranging from 10 ppb to 40 ppm, and the measured detection limit was determined to be equal to 250 ppb under these analytical conditions using ATR-FTIR. The polyisobutylene membrane is promising for pollutant detection in real waters due to the reproducibility of its deposition on selenide materials, the ease of regeneration, the short response time, and the low ppb detection limit, which could be achieved with the infrared photonic microsensor based on chalcogenide materials. To improve the sensitivity of future infrared microsensors, the use of metallic nanostructures on the surface of chalcogenide waveguides appears to be a relevant way, thanks to the plasmon resonance phenomena. Thus, in addition to preliminary surface-enhanced infrared absorption tests using these materials and a functionalization via a self-assembled monolayer of 4-nitrothiophenol, heterostructures combining gold nanoparticles/chalcogenide waveguides have been successfully fabricated with the aim of proposing a SEIRA microsensor device.

Analysis of microplastics in drinking water and other clean water samples with micro-Raman and micro-infrared spectroscopy: minimum requirements and best practice guidelines.

Microplastics are a widespread contaminant found not only in various natural habitats but also in drinking waters. With spectroscopic methods, the polymer type, number, size, and size distribution as well as the shape of microplastic particles in waters can be determined, which is of great relevance to toxicological studies. Methods used in studies so far show a huge diversity regarding experimental setups and often a lack of certain quality assurance aspects. To overcome these problems, this critical review and consensus paper of 12 European analytical laboratories and institutions, dealing with microplastic particle identification and quantification with spectroscopic methods, gives guidance toward harmonized microplastic particle analysis in clean waters. The aims of this paper are to (i) improve the reliability of microplastic analysis, (ii) facilitate and improve the planning of sample preparation and microplastic detection, and (iii) provide a better understanding regarding the evaluation of already existing studies. With these aims, we hope to make an important step toward harmonization of microplastic particle analysis in clean water samples and, thus, allow the comparability of results obtained in different studies by using similar or harmonized methods. Clean water samples, for the purpose of this paper, are considered to comprise all water samples with low matrix content, in particular drinking, tap, and bottled water, but also other water types such as clean freshwater.

Microplastics contamination in pearl-farming lagoons of French Polynesia.

Pearl-farming is the second most important source of income in French Polynesia. However, tropical lagoons are fragile ecosystems with regard to anthropogenic pressures like plastic pollution, which threaten marine life and the pearl oyster-related economy. Here, we investigated the spatial distribution of microplastics (MP) and concentrations in surface water (SW), water column (WC) and cultivated pearl oyster (PO) from three pearl-farming atolls with low population and tourism. Microplastics were categorized by their size class, shape, colour and polymer type identified using FTIR spectroscopy. Widespread MP contamination was observed in every study site (SW, 0.2-8.4 MP m-3; WC, 14.0-716.2 MP m-3; PO, 2.1-125.0 MP g-1 dry weight), with high contamination in the WC highlighting the need to study the vertical distribution of MP, especially as this compartment where PO are reared. A large presence of small (< 200 µm) and fragment-shaped (> 70%) MP suggests that they result from the breakdown of larger plastic debris. The most abundant polymer type was polyethylene in SW (34-39%), WC (24-32%), while in PO, polypropylene (14-20%) and polyethylene were more evenly distributed (9-21%). The most common MP identified as black-grey polyethylene and polypropylene matches the polymer and colour of ropes and collectors questioning a pearl-farming origin.

Toward Chalcogenide Platform Infrared Sensor Dedicated to the In Situ Detection of Aromatic Hydrocarbons in Natural Waters via an Attenuated Total Reflection Spectroscopy Study.

The objective of this study is to demonstrate the successful functionalization of the surface of a chalcogenide infrared waveguide with the ultimate goal of developing an infrared micro-sensor device. First, a polyisobutylene coating was selected by testing its physico-chemical compatibility with a Ge-Sb-Se selenide surface. To simulate the chalcogenide platform infrared sensor, the detection of benzene, toluene, and ortho-, meta- and para-xylenes was efficaciously performed using a polyisobutylene layer spin-coated on 1 and 2.5 µm co-sputtered selenide films of Ge28Sb12Se60 composition deposited on a zinc selenide prism used for attenuated total reflection spectroscopy. The thickness of the polymer coating was optimized by attenuated total reflection spectroscopy to achieve the highest possible attenuation of water absorption while maintaining the diffusion rate of the pollutant through the polymer film compatible with the targeted in situ analysis. Then, natural water, i.e., groundwater, wastewater, and seawater, was sampled for detection measurement by means of attenuated total reflection spectroscopy. This study is a valuable contribution concerning the functionalization by a hydrophobic polymer compatible with a chalcogenide optical sensor designed to operate in the mid-infrared spectral range to detect in situ organic molecules in natural water.

Author Correction: Proteinaceous secretion of bioadhesive produced during crawling and settlement of Crassostrea gigas larvae.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Proteinaceous secretion of bioadhesive produced during crawling and settlement of Crassostrea gigas larvae.

Bioadhesion of marine organisms has been intensively studied over the last decade because of their ability to attach in various wet environmental conditions and the potential this offers for biotechnology applications. Many marine mollusc species are characterized by a two-phase life history: pelagic larvae settle prior to metamorphosis to a benthic stage. The oyster Crassostrea gigas has been extensively studied for its economic and ecological importance. However, the bioadhesive produced by ready to settle larvae of this species has been little studied. The pediveliger stage of oysters is characterized by the genesis of a specific organ essential for adhesion, the foot. Our scanning electron microscopy and histology analysis revealed that in C. gigas the adhesive is produced by several foot glands. This adhesive is composed of numerous fibres of differing structure, suggesting differences in chemical composition and function. Fourier transformed infrared spectroscopy indicated a mainly proteinaceous composition. Proteomic analysis of footprints was able to identify 42 proteins, among which, one uncharacterized protein was selected on the basis of its pediveliger transcriptome specificity and then located by mRNA in situ hybridization, revealing its potential role during substrate exploration before oyster larva settlement.

Macroplastic and microplastic contamination assessment of a tropical river (Saigon River, Vietnam) transversed by a developing megacity.

Both macroplastic and microplastic contamination levels were assessed for the first time in a tropical river estuary system, i.e. the Saigon River, that traverses a developing South East Asian megacity, i.e. Ho Chi Minh City, Vietnam. The analysis of floating debris collected daily on the Nhieu Loc - Thi Nghe canal by the municipal waste management service shows that the plastic mass percentage represents 11-43%, and the land-based plastic debris entering the river was estimated from 0.96 to 19.91 g inhabitant-1 d-1, namely 350 to 7270 g inhabitant-1 yr-1. Microplastics were assessed in the Saigon River and in four urban canals by sampling bulk water for anthropogenic fiber analysis and 300 µm mesh size plankton net exposition for fragment analysis. Fibers and fragments are highly concentrated in this system, respectively 172,000 to 519,000 items m-3 and 10 to 223 items m-3. They were found in various colors and shapes with smallest size and surface classes being predominant. The macroplastics and fragments were mainly made of polyethylene and polypropylene while the anthropogenic fibers were mainly made of polyester. The relation between macroplastic and microplastic concentrations, waste management, population density and water treatment are further discussed.

The antibacterial activity of Magainin I immobilized onto mixed thiols Self-Assembled Monolayers.

An antibacterial peptide, Magainin I, was covalently bound to a mixed 11-mercaptoundecanoïc acid (MUA) and 6-mercaptohexanol (C6OH) (ratio 1:3) Self-Assembled Monolayer (SAM) on gold surfaces. Each step of the surface functionalization was characterized by Polarization Modulation Reflection Absorption InfraRed Spectroscopy (PM-RAIRS) and X-ray Photoelectron Spectroscopy (XPS). The antibacterial activity of the anchored Magainin was tested against three Gram-positive bacteria (Listeria ivanovii, Enterococcus faecalis and Staphylococcus aureus), and the results revealed that the adsorbed Magainin I reduced by more than 50% the adhesion of bacteria at the surface, together with the killing of the bacteria that nonetheless adhered to the surface. No release of the peptide was observed upon contact with the bacterial suspension; the activity has proven to be persistent overtime, up to six months after the first use.

Elaboration of nanohybrid materials by photopolymerisation of 3,4-ethylenedioxythiophene on TiO2.

A method for the elaboration of a heterojunction composed on n-type inorganic semiconducting nanoparticles, TiO(2), and a p-type organic semiconducting polymer poly(3,4-ethylene dioxythiophene) by UV illumination is described.