Sampling of microplastics at a materials recovery facility.

Detecting, separating, and characterizing airborne microplastics from other airborne particulates is currently challenging due to the various instrumental constraints and related sample preparation hurdles that must be overcome. The ability to measure these real-world environments is needed to better assess the risks associated with microplastics. To that end, the current study focused on developing a methodology for sampling and characterizing airborne microplastics. Particulate sampling was carried out at a municipal materials recovery facility near a conveyer belt containing sorted plastic materials to collect airborne environmental particles on filters. Nucleopore filters were mounted on Teflon support rings, coated with 100 nm aluminum to reduce the background signal for micro-Raman spectroscopy, and marked with a fiducial pattern using a laser engraver. The fiducial pattern was crucial in identifying samples, relocating particles, and efficiently enabling orthogonal measurements on the same samples. Optimum sampling conditions of 2 h at 25 L/min were determined using light microscopy to evaluate the particle loadings. The filters were then cut into slices which were attached to sections of thin beryllium-copper sheeting for easy transfer of the filter between microscopy platforms. Scanning electron microscopy was used to identify carbon-rich particles. Light microscopy was used to identify colored particles which were also carbon-rich which were then analyzed using micro-Raman spectroscopy to identify specific polymers.

Microplastics detected in three types of female reproductive organs using micro-Raman spectroscopy.

Microplastics (MPs) are synthetic solid particles or polymer matrices that range in size from 1 µm to 5 mm. MPs are widely present in the global biosphere, leading to increasing concerns about their impact on human health. In this study, micro-Raman spectroscopy was used to evaluate the presence and characteristic of MPs in adenomyosis, ovarian ectopic cysts, and uterine tube tissue samples from 60 females. MPs were detected in all human samples at an average level of 1.5 ± 1.2 particles per g of tissue (Average 1.40 ± 1.11 particles per g of tissue after blank correction.). Among these MPs, a total of 11 polymer types were identified. MPs are mainly composed of polyethylene (PE, 31 %), polypropylene (PP, 22 %) and PE-co-PP (11 %). These MPs had an average length of 15.15 ± 6.45 µm and an average width of 12.56 ± 6.65 µm, with the majority (70 %) measuring less than 20 µm in size. Most MPs were fibers (38.9 %) and fragments (24.4 %). A significant correlation (p <0.05) was found between the sizes of MPs detected across the three disease samples, with PE and PP being the most frequently identified types. This study demonstrates the presence of MPs in diseased tissues from patients with adenomyosis, ovarian ectopic cysts, and uterine tubes, providing evidence for the presence of MPs in reproductive system tissues.

Analysis of Structural Heterogeneity in Low-Rank Coal and Its Pyrolyzed Char Using Multi-Point Scanning Micro-Raman Spectroscopy.

Understanding the changes in carbon structure during the mid-low-temperature pyrolysis of low-rank coal is important for efficient utilization. Raman spectroscopy is commonly used to analyze the structural order of carbonaceous materials, but traditional methods may overlook the heterogeneity of coal/char. This research explores the heterogeneity of char structure derived from low-rank coal at 700 °C through multi-point micro-Raman analysis. The analysis of parameters such as area (A), intensity (I), full width at half maximum (FWHM/W), and peak position (P) reveals that the carbon structure becomes less ordered as coal transforms into char due to the deposition of small molecules on the surface. The study emphasizes the benefits of multi-point detection for gaining in-depth insights into the structural evolution of carbonaceous materials. The increased standard deviation of Raman parameters indicates diverse structural characteristics resulting from pyrolysis at this temperature, which traditional methods may not capture effectively. The mapping method used in this research visually illustrates the distribution of carbon structures in the region.

Degradation Kinetics of Organic-Inorganic Hybrid Materials from Micro-Raman Spectroscopy and Density-Functional Theory: The Case of ß-ZnTe(en)0.5.

Organic-inorganic hybrid materials often face a stability challenge. ß-ZnTe(en)0.5 , which uniquely has over 15-year real-time degradation data, is taken as a prototype structure to demonstrate an accelerated thermal aging method for assessing the intrinsic and ambient-condition long-term stability of hybrid materials. Micro-Raman spectroscopy is used to investigate the thermal degradation of ß-ZnTe(en)0.5 in a protected condition and in air by monitoring the temperature dependences of the intrinsic and degradation-product Raman modes. First, to understand the intrinsic degradation mechanism, the transition state of the degradation is identified, then using a density functional theory, the intrinsic energy barrier between the transition state and ground state is calculated to be 1.70 eV, in excellent agreement with the measured thermal degradation barrier of 1.62 eV in N2 environment. Second, for the ambient-condition degradation, a reduced thermal activation barrier of 0.92 eV is obtained due to oxidation, corresponding to a projected ambient half-life of 40 years at room temperature, in general agreement with the experimental observation of no apparent degradation over 15 years. Furthermore, the study reveals a mechanism, conformation distortion enhanced stability, which plays a pivotal role in forming the high kinetic barrier, contributing greatly to the impressive long-term stability of ß-ZnTe(en)0.5 .

Vibrational spectroscopy identifies myocardial chemical modifications in heart failure with preserved ejection fraction.

BACKGROUND: Vibrational spectroscopy can be a valuable tool to monitor the markers of cardiovascular diseases. In the present work, we explored the vibrational spectroscopy characteristics of the cardiac tissue in an experimental model of heart failure with preserved ejection fraction (HFpEF). The goal was to detect early cardiac chemical modifications associated with the development of HFpEF. METHODS: We used the Fourier-transform infrared (FTIR) and Raman micro-spectroscopic techniques to provide complementary and objective tools for the histological assessment of heart tissues from an animal model of HFpEF. A new sampling technique was adopted (tissue print on a CaF2 disk) to characterize the extracellular matrix. RESULTS: Several spectroscopic markers (lipids, carbohydrates, and glutamate bands) were recognized in the cardiac ventricles due to the comorbidities associated with the pathology, such as obesity and diabetes. Besides, abnormal collagen cross-linking and a decrease in tryptophan content were observed and related to the stiffening of ventricles and to the inflammatory state which is a favourable condition for HFpEF. CONCLUSIONS: By the analyses of tissues and tissue prints, FTIR and Raman techniques were shown to be highly sensitive and selective in detecting changes in the chemistry of the heart in experimental HFpEF and its related comorbidities. Vibrational spectroscopy is a new approach that can identify novel biomarkers for early detection of HFpEF.

A Study of Pigment, Adhesive, and Firing Temperature in Pottery Figurines Excavated from the Tomb of Qibi Ming, China.

Some painted pottery figurines were excavated from the tomb of Qibi Ming of the Tang Dynasty. A series of analytical techniques were employed to understand the craftsmanship of these painted pottery figurines. The pigment, cross-section, adhesive, and firing temperature were analyzed using microscopy (OM), energy X-ray fluorescence spectrometry (EDX), micro-Raman spectroscopy, pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS), and a dilatometer (DIL). The results demonstrated that the surface of the pigment layers had degraded to different degrees. The pigment particles were litharge, gypsum, malachite, cinnabar, hematite, minium, white lead, and carbon black. The cross-sectional images show that the painted layer of figurines 10-0966 and 10-0678 included a pigment layer and a preparation layer. The preparation layer of both pigments was lead white. Animal glue was used as an adhesive. The firing temperature of the pottery figurines was likely 1080 °C. This study can provide more accurate information with regard to the composition of the raw materials utilized in the making of these artifacts and support the selection of appropriate substances for the purposes of conservation and restoration of the painted pottery figurines.

Raman Spectra and Ancient Life: Vibrational ID Profiles of Fossilized (Bone) Tissues.

Raman micro-spectroscopy is a non-destructive and non-contact analytical technique that combines microscopy and spectroscopy, thus providing a potential for non-invasive and in situ molecular identification, even over heterogeneous and rare samples such as fossilized tissues. Recently, chemical imaging techniques have become an increasingly popular tool for characterizing trace elements, isotopic information, and organic markers in fossils. Raman spectroscopy also shows a growing potential in understanding bone microstructure, chemical composition, and mineral assemblance affected by diagenetic processes. In our lab, we have investigated a wide range of different fossil tissues, mainly of Mesozoic vertebrates (from Jurassic through Cretaceous). Besides standard spectra of sedimentary rocks, including pigment contamination, our Raman spectra also exhibit interesting spectral features in the 1200-1800 cm-1 spectral range, where Raman bands of proteins, nucleic acids, and other organic molecules can be identified. In the present study, we discuss both a possible origin of the observed bands of ancient organic residues and difficulties with definition of the specific spectral markers in fossilized soft and hard tissues.

Using Micro-Raman Spectroscopy to Investigate Chemical Composition, Mixing States, and Heterogeneous Reactions of Individual Atmospheric Particles.

Measuring the chemical composition of individual atmospheric aerosol particles can provide direct evidence of their heterogeneous reactions and mixing states in the atmosphere. In this study, micro-Raman spectroscopy was used to measure the chemical composition of 1200 individual atmospheric particles in 11 samples collected in Beijing air. (NH4)2SO4, NH4NO3, various minerals, carbonaceous species (soot and organics), and NaNO3 were identified in the measured particles according to their characteristic Raman peaks. These species represented the main components of aerosol particles. In individual particles, NH4NO3 and (NH4)2SO4 either existed separately or were internally mixed. Possible reaction pathways of CaCO3 particles in the atmosphere were proposed based on the results of this study and laboratory simulations on heterogeneous reactions in the literature. CaCO3 reacted with N- and S-containing (nitrogen- and sulfur-containing) acidic gases to produce Ca(NO3)2 and CaSO4. Ca(NO3)2 further reacted with S-containing acidic gases and oxidants to produce CaSO4. Of the soot-containing particles, 23% were internal mixtures of soot and inorganic material. Of the organics-containing particles, 57% were internal mixtures of organic and inorganic materials. Micro-Raman spectroscopy directly identified functional groups and molecules in individual atmospheric particles under normal ambient conditions, rendering it a powerful tool for measuring the chemical composition of individual atmospheric particles with a diameter of ≥1.0 µm.

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.

Application of Multispectral Imaging and Portable Spectroscopic Instruments to the Analysis of an Ancient Persian Illuminated Manuscript.

Illuminated manuscripts are, in general, the final products of a wise and complex interaction of different competencies. In particular, each manuscript reflects uses and techniques rooted in the historical and geographical traditions of the area of realization. Defining the characteristics and the materials in these valuable artefacts is an essential element to reconstruct their history and allow a more precise collocation and a possible comparison with other works in similar periods and areas. Non-invasive methods, mainly using portable instruments, offer undoubtedly good support in these studies. Recent analyses of an ancient Persian illuminated manuscript, combining multispectral imaging and spectroscopic measurements made with portable instruments (XRF, FORS, micro-Raman, IR-ATR) on selected points, provided new data for an improved understanding of this rare book. This study details the possibilities offered by combining these non-invasive methods for an in-depth understanding of the techniques and practices behind the realization of Middle Eastern illuminated manuscripts and provided new perspectives for multidisciplinary approaches to research in this field.

Fe(II) Spin Crossover/Polymer Hybrid Materials: Investigation of the SCO Behavior via Temperature-Dependent Raman Spectroscopy, Physicochemical Characterization and Migration Release Study.

Polymeric composites constitute an appealing class of materials with applications in various fields. Spin crossover (SCO) coordination complexes are switchable materials with potential use in data storage and sensors. Their incorporation into polymers can be considered an effective method for their wider practical application. In this study, Fe(II) SCO/polylactic acid hybrid polymeric composites have been prepared by film casting. The mononuclear coordination complex [Fe{N(CN)2}2(abpt)2] was incorporated into polylactic acid. The morphological, structural and thermoanalytical characterization of the composite films were performed via scanning electron microscopy (SEM), attenuated total reflectance (ATR/FTIR), Raman spectroscopy and differential scanning calorimetry (DSC). In addition, the migration release study (MRS) of the SCO compound from the polymeric matrix into the food simulant 50% v/v water/ethanol solution was also examined via UV/Vis absorption. Of particular interest was the investigation of the SCO behavior of the coordination complex after its incorporation into the polymer matrix; it was accomplished by temperature-dependent micro-Raman spectroscopy. The described attempt could be considered a preparatory step toward the development of SCO-based temperature sensors integrated into food packaging materials.

Micro-Raman Characterization of Structural Features of High-k Stack Layer of SOI Nanowire Chip, Designed to Detect Circular RNA Associated with the Development of Glioma.

The application of micro-Raman spectroscopy was used for characterization of structural features of the high-k stack (h-k) layer of "silicon-on-insulator" (SOI) nanowire (NW) chip (h-k-SOI-NW chip), including Al2O3 and HfO2 in various combinations after heat treatment from 425 to 1000 °C. After that, the NW structures h-k-SOI-NW chip was created using gas plasma etching optical lithography. The stability of the signals from the monocrine phase of HfO2 was shown. Significant differences were found in the elastic stresses of the silicon layers for very thick (>200 nm) Al2O3 layers. In the UV spectra of SOI layers of a silicon substrate with HfO2, shoulders in the Raman spectrum were observed at 480-490 cm-1 of single-phonon scattering. The h-k-SOI-NW chip created in this way has been used for the detection of DNA-oligonucleotide sequences (oDNA), that became a synthetic analog of circular RNA-circ-SHKBP1 associated with the development of glioma at a concentration of 1.1 × 10-16 M. The possibility of using such h-k-SOI NW chips for the detection of circ-SHKBP1 in blood plasma of patients diagnosed with neoplasm of uncertain nature of the brain and central nervous system was shown.

Compositional Control as the Key for Achieving Highly Efficient OER Electrocatalysis with Cobalt Phosphates Decorated Nanocarbon Florets.

Compositional interplay of two different cobalt phosphates (Co(H2 PO4 )2 ; Co-DP and Co(PO3 )2 ; Co-MP) loaded on morphologically engineered high surface area nanocarbon leads to an increased electrocatalytic efficiency for oxygen evolution reaction (OER) in near neutral conditions. This is reflected as significant reduction in the onset overpotential (301 mV) and enhanced current density (30 mA cm-2 @ 577 mV). In order to achieve uniform surface loading, organic-soluble thermolabile cobalt-bis(di-tert-butylphosphate) is synthesized in situ inside the nanocarbon matrix and subsequently pyrolyzed at 150 °C to produce Co(H2 PO4 )2 /Co(PO3 )2 (80:20 wt%). Annealing this sample at 200 or 250 °C results in the redistribution of the two phosphate systems to 55:45 or 20:80 (wt%), respectively. Detailed electrochemical measurements clearly establish that the 55:45 (wt%) sample prepared at 200 °C performs the best as a catalyst, owing to a relay mechanism that enhances the kinetics of the 4e- transfer OER process, which is substantiated by micro-Raman spectroscopic studies. It is also unraveled that the engineered nanocarbon support simultaneously enhances the interfacial charge-transfer pathway, resulting in the reduction of onset overpotential, compared to earlier investigated cobalt phosphate systems.

Thermal Expansion Coefficient of Monolayer Molybdenum Disulfide Using Micro-Raman Spectroscopy.

Atomically thin two-dimensional (2D) materials have shown great potential for applications in nanoscale electronic and optical devices. A fundamental property of these 2D flakes that needs to be well-characterized is the thermal expansion coefficient (TEC), which is instrumental to the dry transfer process and thermal management of 2D material-based devices. However, most of the current studies of 2D materials' TEC extensively rely on simulations due to the difficulty of performing experimental measurements on an atomically thin, micron-sized, and optically transparent 2D flake. In this work, we present a three-substrate approach to characterize the TEC of monolayer molybdenum disulfide (MoS2) using micro-Raman spectroscopy. The temperature dependence of the Raman peak shift was characterized with three different substrate conditions, from which the in-plane TEC of monolayer MoS2 was extracted on the basis of lattice symmetries. Independently from two different phonon modes of MoS2, we measured the in-plane TECs as (7.6 ± 0.9) × 10-6 K-1 and (7.4 ± 0.5) × 10-6 K-1, respectively, which are in good agreement with previously reported values based on first-principle calculations. Our work is not only useful for thermal mismatch reduction during material transfer or device operation but also provides a general experimental method that does not rely on simulations to study key properties of 2D materials.

Applications of Raman spectroscopic techniques for quality and safety evaluation of milk: A review of recent developments.

Milk is a complete nutrient source for humans. The quality and safety of milk are critical for both producers and consumers, thereby the dairy industry requires rapid and nondestructive methods to ensure milk quality and safety. However, conventional methods are time-consuming and laborious, and require complicated preparation procedures. Therefore, the exploration of new milk analytical methods is essential. This current review introduces the principles of Raman spectroscopy and presents recent advances since 2012 of Raman spectroscopic techniques mainly involving surface-enhanced Raman spectroscopy (SERS), fourier-transform (FT) Raman spectroscopy, near-infrared (NIR) Raman spectroscopy, and micro-Raman spectroscopy for milk analysis including milk compositions, microorganisms and antibiotic residues in milk, as well as milk adulterants. Additionally, some challenges and future outlooks are proposed. The current review shows that Raman spectroscopic techniques have the promising potential for providing rapid and nondestructive detection of milk parameters. However, the application of Raman spectroscopy on milk analysis is not common yet since some limitations of Raman spectroscopy need to be overcome before making it a routine tool for the dairy industry.

A micro-Raman and chemometric study of urinary tract infection-causing bacterial pathogens in mixed cultures.

Detection of urinary tract infection (UTI)-causing bacteria uses conventional time-consuming microbiological techniques. The current need is to use a fast and reliable method of bacterial identification. In order to unambiguously distinguish the UTI-causing five bacterial species used in the current study, micro-Raman spectra were obtained from a home-assembled micro-Raman system and analyzed by multivariate statistical techniques such as principal component analysis (PCA), partial least square-discriminate analysis (PLS-DA), and support vector machine (SVM). Also, the micro-Raman spectra recorded from samples containing two and three bacterial species were tested and validated against the aforementioned calibration models using PLS-DA and SVM. The prediction accuracies of up to 73 and 89% were achieved with PLS-DA and SVM, respectively. Taken together, the present study depicts the capturing of unique micro-Raman spectral features manifesting from the biochemical content of each bacterium. Also, micro-Raman spectroscopy combined with multivariate data analysis can therefore be a reliable and faster technique for the diagnosis of UTI-causing bacteria. Graphical Abstract.

Multiple pathways of crystal nucleation in an extremely supersaturated aqueous potassium dihydrogen phosphate (KDP) solution droplet.

Solution studies have proposed that crystal nucleation can take more complex pathways than previously expected in classical nucleation theory, such as formation of prenucleation clusters or densified amorphous/liquid phases. These findings show that it is possible to separate fluctuations in the different order parameters governing crystal nucleation, that is, density and structure. However, a direct observation of the multipathways from aqueous solutions remains a great challenge because heterogeneous nucleation sites, such as container walls, can prevent these paths. Here, we demonstrate the existence of multiple pathways of nucleation in highly supersaturated aqueous KH2PO4 (KDP) solution using the combination of a containerless device (electrostatic levitation), and in situ micro-Raman and synchrotron X-ray scattering. Specifically, we find that, at an unprecedentedly deep level of supersaturation, a high-concentration KDP solution first transforms into a metastable crystal before reaching stability at room temperature. However, a low-concentration solution, with different local structures, directly transforms into the stable crystal phase. These apparent multiple pathways of crystallization depend on the degree of supersaturation.

Graphene-Based Raman Spectroscopy for pH Sensing of X-rays Exposed and Unexposed Culture Media and Cells.

Graphene provides a unique way of sensing the local pH level of substances on the micrometric scale, with important implications for the monitoring of cellular metabolic activities where proton excretion could occur. Accordingly, an innovative biosensing approach for the quantification of the pH value of biological fluids, to be used also with small amounts of fluids, was realized and tested. It is based on the use of micro-Raman spectroscopy to detect the modifications of the graphene doping level induced by the contact of the graphene with the selected fluids. The approach was preliminarily tested on aqueous solutions of known pH values. It was then used to quantify the pH values of cell culture media directly exposed to different doses of X-ray radiation and to media exposed to X-ray-irradiated cells. The Raman response of cells placed on graphene layers was also examined.

Using X-ray computed tomography and micro-Raman spectrometry to measure individual particle surface area, volume, and morphology towards investigating atmospheric heterogeneous reactions.

Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography (XCT) and micro-Raman spectrometry to measure individual CaCO3 particle morphology, with sizes ranging from 3.5-6.5µm. Particle surface area and volume were calculated using a reconstruction method based on software three-dimensional (3-D) rendering. The XCT was first validated with high-resolution field-emission scanning electron microscopy (FE-SEM) to acquire accurate CaCO3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual CaCO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.

Seasonal variation and chemical composition of particulate matter: A study by XPS, ICP-AES and sequential microanalysis using Raman with SEM/EDS.

During the winter period (January-March 2016), the total suspended particles (TSP) and particulate matter smaller than 2.5µm (PM2.5) were characterized by the application of various analytical techniques in four zones of the Metropolitan Area of Monterrey in Mexico. To evaluate the seasonal variation of some elements in the particulate matter, the results of this study were compared with those obtained during the summer season (July-September 2015). The speciation of the C1s signal by X-ray photoelectron spectroscopy revealed the contribution of aromatic and aliphatic hydrocarbons as the main components in both seasons. Conversely, carboxylic groups associated with biogenic emissions were detected only in winter. The percentages of SO42- ions were lower in winter, possibly caused by the decrease in the solar radiation, and relative humidity recorded. The results of the ICP analysis revealed that Fe, Zn and Cu were the most abundant metals in both TSP and PM2.5 in the two seasons. There were significant seasonal variations for concentrations of As, Ni and Zn in the urban area and for Fe, As, Cd, Ni and Zn in the industrial zone. This was attributed to the greater burning of fuels as well as to an increase in vehicular traffic, the effect of thermal inversion and changes in some meteorological parameters. The results of the sequential microanalysis by Raman spectroscopy and SEM/EDS allowed observation of deposits of carbonaceous material on the particles and to perform the speciation of particles rich in Fe and Pb, which helped infer their possible emission sources.