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.

Diazonium Salt-Based Surface-Enhanced Raman Spectroscopy Nanosensor: Detection and Quantitation of Aromatic Hydrocarbons in Water Samples.

Here, we present a surface-enhanced Raman spectroscopy (SERS) nanosensor for environmental pollutants detection. This study was conducted on three polycyclic aromatic hydrocarbons (PAHs): benzo[a]pyrene (BaP), fluoranthene (FL), and naphthalene (NAP). SERS substrates were chemically functionalized using 4-dodecyl benzenediazonium-tetrafluoroborate and SERS analyses were conducted to detect the pollutants alone and in mixtures. Compounds were first measured in water-methanol (9:1 volume ratio) samples. Investigation on solutions containing concentrations ranging from 10-6 g L-1 to 10-3 g L-1 provided data to plot calibration curves and to determine the performance of the sensor. The calculated limit of detection (LOD) was 0.026 mg L-1 (10-7 mol L-1) for BaP, 0.064 mg L-1 (3.2 × 10-7 mol L-1) for FL, and 3.94 mg L-1 (3.1 × 10-5 mol L-1) for NAP, respectively. The correlation between the calculated LOD values and the octanol-water partition coefficient (Kow) of the investigated PAHs suggests that the developed nanosensor is particularly suitable for detecting highly non-polar PAH compounds. Measurements conducted on a mixture of the three analytes (i) demonstrated the ability of the developed technology to detect and identify the three analytes in the mixture; (ii) provided the exact quantitation of pollutants in a mixture. Moreover, we optimized the surface regeneration step for the nanosensor.

Harmful algae and pathogens on plastics in three mediterranean coastal lagoons.

Plastic is now a pervasive pollutant in all marine ecosystems. The microplastics and macroplastic debris were studied in three French Mediterranean coastal lagoons (Prevost, Biguglia and Diana lagoons), displaying different environmental characteristics. In addition, biofilm samples were analyzed over the seasons to quantify and identify microalgae communities colonizing macroplastics, and determine potentially harmful microorganisms. Results indicate low but highly variable concentrations of microplastics, in relation to the period and location of sampling. Micro-Raman spectroscopy analyses revealed that the majority of macroplastic debris corresponded to polyethylene (PE) and low-density polyethylene (LDPE), and to a far lesser extent to polypropylene (PP). The observations by Scanning Electron Microscopy of microalgae communities colonizing macroplastic debris demonstrated differences depending on the seasons, with higher amounts in spring and summer, but without any variation between lagoons and polymers. Among the Diatomophyceae, the most dominant genera were Amphora spp., Cocconeis spp., and Navicula spp.. Cyanobacteria and Dinophyceae such as Prorocentrum cordatum, a potentially toxic species, were also found sporadically. The use of Primer specific DNA amplification tools enabled us to detect potentially harmful microorganisms colonizing plastics, such as Alexandrium minutum or Vibrio spp. An additional in situ experiment performed over one year revealed an increase in the diversity of colonizing microalgae in relation to the duration of immersion for the three tested polymers PE, LDPE and polyethylene terephthalates (PET). Vibrio settled durably after two weeks of immersion, whatever the polymer. This study confirms that Mediterranean coastal lagoons are vulnerable to the presence of macroplastic debris that may passively host and transport various species, including some potentially harmful algal and bacterial microorganisms.

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.

Microplastic contamination and pollutant levels in mussels and cockles collected along the channel coasts.

Nowadays, environmental pollution by microplastics (<5 mm; MP) is a major issue. MP are contaminating marine organisms consumed by humans. This work studied MP contamination in two bivalve species of commercial interest: blue mussel (Mytilus edulis) and common cockle (Cerastoderma edule) sampled on the Channel coastlines (France). In parallel, 13 plastic additives and 27 hydrophobic organic compounds (HOC) were quantified in bivalves flesh using SBSE-TD-GS-MS/MS to explore a possible relationship between their concentrations and MP contamination levels. MP were extracted using a 10% potassium hydroxide digestion method then identified by µ-Raman spectroscopy. The proportion of contaminated bivalves by MP ranged from 34 to 58%. Blue mussels and common cockles exhibited 0.76 ±â€¯0.40 and 2.46 ±â€¯1.16 MP/individual and between 0.15 ±â€¯0.06 and 0.74 ±â€¯0.35 MP/g of tissue wet weight. Some HOC and plastic additives were detected in bivalves. However, no significant Pearson or Spearman correlation was found between MP loads and plastic additives or HOC concentrations in bivalve tissues for the two species.

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.

Microplastic bacterial communities in the Bay of Brest: Influence of polymer type and size.

Microplastics (<5 mm) exhibit intrinsic features such as density, hydrophobic surface, or high surface/volume ratio, that are known to promote microbial colonization and biofilm formation in marine ecosystems. Yet, a relatively low number of studies have investigated the nature of microplastic associated bacterial communities in coastal ecosystems and the potential factors influencing their composition and structure. Here, we characterized microplastics collected in the Bay of Brest by manual sorting followed by Raman spectroscopy and studied their associated bacterial assemblages using 16S amplicon high-throughput sequencing. Our methodology allowed discriminating polymer type (polyethylene, polypropylene and polystyrene) within small size ranges (0.3-1 vs. 1-2 vs. 2-5 mm) of microplastics collected. Data showed high species richness and diversity on microplastics compared to surrounding seawater samples encompassing both free living and particle attached bacteria. Even though a high proportion of operational taxonomic units (OTU; 94 ±â€¯4%) was shared among all plastic polymers, polystyrene fragments exhibited distinct bacterial assemblages as compared to polyethylene and polypropylene samples. No effect of microplastic size was revealed regardless of polymer type, site and date of collection. The Vibrio genus was commonly detected in the microplastic fraction and specific PCR were performed to determine the presence of potentially pathogenic Vibrio strains (namely V. aestuarianus and the V. splendidus polyphyletic group). V. splendidus related species harboring putative oyster pathogens were detected on most microplastic pools (77%) emphasizing the need of further research to understand the role of microplastics on pathogen population transport and ultimate disease emergence.

Organometallic nanoprobe to enhance optical response on the polycyclic aromatic hydrocarbon benzo[a]pyrene immunoassay using SERS technology.

We demonstrated the use of a new organometallic nanoprobe for competitive surface-enhanced Raman scattering (SERS) immunoassay devoted to the detection of polycyclic aromatic hydrocarbons (PAH) such as benzo[a]pyrene (BaP) in seawater. The nanoprobes are gold nanoparticles (GNPs) labeled by a Raman reporter, the 5,5'-dithiobis(succinimidyl-2-nitrobenzoate) (DSNB) and functionalized with monoclonal antibodies anti-BaP. The antibodies are bound with a high specificity to the analyte while the GNPs enhanced the Raman scattering of the DSNB. This type of immunoassay involved the grafting of BaP onto a sensing surface. Thus, NH2-terminated self-assembled monolayer is formed on the surface of gold substrate using cysteamine. Amines finally reacted with 6-formylbenzo[a]pyrene. So, this SERS detection involves four steps: (i) the nanoprobes are incubated with the sample; (ii) a drop of the mixture is then put onto the substrate; (iii) the surface is rinsed; and (iv) the surface is analyzed by Raman spectroscopy. To synthesize the nanoprobes, firstly, we prepared GNPs according to Frens' method. Then, GNPs were spontaneously labeled by the DSNB Raman reporter, thanks to a strong gold-sulfur interaction. Thereafter, BaP antibodies were cross-linked to the DSNB labeled GNPs by reaction of proteins primary amino groups with N-hydroxyl succinimide (NHS). Before use in SERS detection, their activity was controlled by surface plasmon resonance technique. The present method allows us to detect BaP at trace concentration (2 nmol/L). The results demonstrate that the proposed method has a great potential for application in the monitoring of seawater.

Investigation of aromatic hydrocarbon inclusion into cyclodextrins by Raman spectroscopy and thermal analysis.

Among various cavitand molecules, cyclodextrins are extensively studied due to their ability to form host-guest complexes with small hydrophobic molecules. Aiming to explore cyclodextrin implementation on the scopes related to the environmental pollution monitoring or remediation, extensive studies for understanding the cyclodextrin-based host-guest complex formation with selected targeted substances are conducted. In this context, two polycyclic aromatic hydrocarbons, naphthalene and fluoranthene as well as toluene as a member of volatile organic compounds, were studied regarding their ability to encapsulate into cyclodextrin cavities. Synthesised complexes were examined by thermogravimetric analysis combined with Raman spectroscopy. The obtained results demonstrated that the size between targeted molecules and the cyclodextrin cavities strongly correlates with its ability to engage in complexation. Thus, this latter parameter plays an important role in the inclusion complex formation as well as in the strength of the interaction between the molecules.

Microplastics in seafood: Benchmark protocol for their extraction and characterization.

Pollution of the oceans by microplastics (<5 mm) represents a major environmental problem. To date, a limited number of studies have investigated the level of contamination of marine organisms collected in situ. For extraction and characterization of microplastics in biological samples, the crucial step is the identification of solvent(s) or chemical(s) that efficiently dissolve organic matter without degrading plastic polymers for their identification in a time and cost effective way. Most published papers, as well as OSPAR recommendations for the development of a common monitoring protocol for plastic particles in fish and shellfish at the European level, use protocols containing nitric acid to digest the biological tissues, despite reports of polyamide degradation with this chemical. In the present study, six existing approaches were tested and their effects were compared on up to 15 different plastic polymers, as well as their efficiency in digesting biological matrices. Plastic integrity was evaluated through microscopic inspection, weighing, pyrolysis coupled with gas chromatography and mass spectrometry, and Raman spectrometry before and after digestion. Tissues from mussels, crabs and fish were digested before being filtered on glass fibre filters. Digestion efficiency was evaluated through microscopical inspection of the filters and determination of the relative removal of organic matter content after digestion. Five out of the six tested protocols led to significant degradation of plastic particles and/or insufficient tissue digestion. The protocol using a KOH 10% solution and incubation at 60 °C during a 24 h period led to an efficient digestion of biological tissues with no significant degradation on all tested polymers, except for cellulose acetate. This protocol appeared to be the best compromise for extraction and later identification of microplastics in biological samples and should be implemented in further monitoring studies to ensure relevance and comparison of environmental and seafood product quality studies.

Hydration of a synthetic clay with tetrahedral charges: a multidisciplinary experimental and numerical study.

The interaction of water with a synthetic saponite clay sample, with a layer charge of 1 per unit cell (0.165 C m(-2)), was investigated by following along water adsorption and desorption in the relative pressure range from 10(-6) to 0.99 (i) the adsorbed amount by gravimetric and near-infrared techniques, (ii) the basal distance and arrangement of water molecules in the interlayer by X-ray and neutron diffraction under controlled water pressure, and (iii) the molecular structure and interaction of adsorbed water molecules by near-infrared (NIR) and Raman spectroscopy under controlled water pressure. The results thus obtained were confronted with Grand Canonical Monte Carlo (GC/MC) simulations. Using such an approach, various well-distinct hydration ranges can be distinguished. In the two first ranges, at low water relative pressure, adsorption occurs on external surfaces only, with no swelling associated. The next range corresponds to the adsorption of water molecules around the interlayer cation without removing it from its position on top of the ditrigonal cavity of the tetrahedral layer and is associated with limited swelling. In the following range, the cation is displaced toward the mid-interlayer region. The interlamellar spacing thus reached, around 12.3 A, corresponds to what is classically referred to as a "one-layer hydrate," whereas no water layer is present in the interlayer region. The next hydration range corresponds to the filling of the interlayer at nearly constant spacing. This leads to the formation of a well-organized network of interlayer water molecules with significant interactions with the clay layer. The structure thus formed leads to a complete extinction of the d001 line in D2O neutron diffraction patterns that are correctly simulated by directly using the molecular configurations derived by GC/MC. The next range (0.50 < P/P0 < 0.80) corresponds to the final swelling of the structure to reach d spacing values of 15.2 A (usually referred to the "two-layer hydrate"). It is associated with the development of a network of liquidlike water molecules more structured than in bulk water. The final hydration range at high relative pressure mainly corresponds to the filling of pores between clay particles.

First steps of in situ surface-enhanced Raman scattering during shipboard experiments.

It is shown that the surface-enhanced Raman scattering (SERS) technique can be applied to detect organic molecules during in situ experiments. To this purpose, we used trans-1,2-bis(4-pyridyl)ethylene (BPE) as a target molecule. Adsorbed on the SERS chemosensor surface and excited under laser, the vibration modes of the molecules can be identified. SERS chemosensors are based on quartz substrates functionalized by silanization and partially coated with gold nanoparticles. SERS measurements during shipboard experiments were made with a home-made in situ Raman spectrometer connected to a marinized micro-fluidic system. The device was designed to host chemosensors in order to ensure measurements with a flow cell. A theoretical limit of detection was estimated in the range of picomolar (pM) concentrations based on Freundlich isotherm calculations.

Detection of polycyclic aromatic hydrocarbon (PAH) compounds in artificial sea-water using surface-enhanced Raman scattering (SERS).

This paper reports an accurate synthesis of surface-enhanced Raman scattering (SERS) active substrates, based on gold colloidal monolayer, suitable for in situ environmental analysis. Quartz substrates were functionalized by silanization with (3-mercaptopropyl)trimethoxysilane (MPMS) or (3-aminopropyl)trimethoxysilane (APTMS) and they subsequently reacted with colloidal suspension of gold metal nanoparticles: respectively, the functional groups SH and NH(2) bound gold nanoparticles. Gold nanoparticles were prepared by the chemical reduction of HAuCl(4) using sodium tricitrate and immobilized onto silanized quartz substrates. Active substrate surface morphology was characterized with scanning electron microscopy (SEM) measurements and gold nanoparticles presented a diameter in the range 40-100 nm. Colloidal hydrophobic films, allowing nonpolar molecule pre-concentration, were obtained. The surfaces exhibit strong enhancement of Raman scattering from molecules adsorbed on the films. Spectra were recorded for two PAHs, naphthalene and pyrene, in artificial sea-water (ASW) with limits of detection (LODs) of 10 ppb for both on MPMS silanized substrates.