Spectroscopy Research Articles

First-principles molecular dynamics of exciton-driven initial stage of plasma phase transition in warm dense molecular nitrogen.

Understanding the properties of molecular nitrogen N2 at extreme conditions is the fundamental problem for atomistic theory and the important benchmark for the capabilities of first-principles molecular dynamics (FPMD) methods. In this work, we focus on the connection between the dynamics of ions and electronic excitations in warm dense N2. The restricted open-shell Kohn-Sham method gives us the possibility to reach relevant time and length scales for FPMD modeling of an isolated exciton dynamics in warm dense N2. Wannier localization sheds light on the corresponding mechanisms of covalent bond network rearrangements that stand behind polymerization kinetics. FPMD results suggest a concept of energy transfer from the thermal energy of ions into the internal energy of polymeric structures that form in warm dense N2 at extreme conditions. Our findings agree with the thermobaric conditions for the onset of absorption in the optical spectroscopy study of Jiang et al. [Nat. Commun. 9, 2624 (2018)].

Urine-based SERS and multivariate statistical analysis for identification of non-muscle-invasive bladder cancer and muscle-invasive bladder cancer.

Bladder cancer (BC) is an epidemiological urologic malignancy that continues to increase each year. Early diagnosis and prognosis monitoring is always significant in clinical practice, especially in distinguishing non-muscle-invasive bladder cancer (NMIBC) from muscle-invasive bladder cancer (MIBC), due to the various depths of tumor invasion related to different therapeutic schedules and recurrence rates. Common diagnostic approaches are too invasive or generally inefficient in accuracy and specificity. In this work, a totally non-invasive and cost-effective method is established by investigating urine samples using surface-enhanced Raman spectroscopy (SERS) and multivariate statistical analysis. The comparison of urine SERS spectra shows the intensities of characteristic peaks for DNA/RNA, hypoxanthine, albumin, D-( +)-galactosamine, fatty acids, and some amino acids are distinguishable in BC occurrence and invasion progression. A PLS-LDA-based two-step binary classification scheme is performed on urine SERS spectra and the diagnostic accuracies were 97.7% and 96.3% for healthy individuals versus BC patients and NMIBC versus MIBC patients, respectively. Moreover, the impact of urine SERS spectral lengths in reaching high-precision recognition of BC is investigated. The results show that the Raman peaks at 803, 893, 1139, 1375, and 1466cm-1 play an essential role in correctly categorizing healthy control, NMIBC, and MIBC patients, and SERS spectra ranges from 400 to 1600cm-1 are enough for this identification task. These findings provide a sensitive, label-free, rapid, and totally non-invasive way for assessment of invasion depth of BC to its early diagnosis and prognosis monitoring, as well as valuable insights for selecting reasonable spectral range to enhance the measurement efficiency especially in large-scale sample datasets.

Dispersion and self-assembly of 2,5-dimercapto-1,3,4-thiadiazole (DMTD) functionalized silver QDs in 6 CHBT liquid crystal

ABSTRACT Silver nanoparticles were synthesised using silver nitrate and tri-sodium citrate and were functionalized with 2,5-Dimercapto-1,3,4-thiadiazole (DMTD) linking molecules. Functionalized silver nanoparticles dispersed within 4-(trans-4-n hexylcyclohexyl) isothiocyanatobenzoate (6CHBT) liquid crystal (LC) matrices have attracted significant attention because of their potential for tailoring tuneable surface plasmonic, optical, and electronic properties by controlling the self-assembly of silver dots. The unique combination of functionalized nanoparticles and 6CHBT LCs offers a versatile platform for manipulating interactions at the nanoscale. The dispersion of functionalized Ag nanoparticles within the LCs appears to substantially modify the plasmonic and opto-electronic properties of the Ag QDs. The formation and morphology of the self-assembled structures of silver nanoparticles were confirmed by Optical and Scanning Electron Microscopy. Optical microscopy (OM) and Scanning Electron Microscopy (SEM) images of Ag-doped 6CHBT confirmed the formation of nano-micro spheres, as well as ring and rod-like structures in LC media. We have used High-Resolution X-ray diffraction (HR-XRD), Fourier-Transform Infrared Spectroscopy (FTIR), Surface-Enhanced Raman Spectroscopy (SERS), Optical Microscopy (OM), Scanning Electron Microscopy (SEM), Ultraviolet-visible-near-infrared Spectroscopy (UV-Vis-NIR), and Fluorescence (FL) Spectroscopy. We calculated the electronic properties such as the bandgap of the synthesised Ag QDs and functionalized Ag QDs using UV-Vis-NIR and Tauc’s plot curves. Surface-enhanced Raman spectroscopy, Optical microscopy, SEM, and UV-Vis-NIR spectral data were used to correlate the properties of the LC and QDs hybrid systems.

Applying Machine Learning and SERS for Precise Typing of DNA Secondary Structures.

Surface-enhanced Raman spectroscopy (SERS) has been demonstrated as an effective method for elucidating secondary structural characteristics of DNA. However, the inherent complexity of the DNA conformation and the lack of SERS samples pose challenges for identifying numerous secondary structures. To address these issues, a synergistic method integrating machine learning with SERS was proposed so as to analyze the SERS spectra of 54 well-defined conformational oligonucleotides, namely, G-quadruplex (G4), i-motif (iM), double-strand (DS), and single-strand (SS) configurations. Principal component analysis (PCA) effectively segregated the oligonucleotides into three distinct conformational groups (G4s, iMs, and others). Furthermore, linear discriminant analysis (LDA), K-nearest neighbor (KNN), and support vector machine (SVM) approaches were utilized to improve the typing accuracy of 54 trained sequences. This enabled the correct classification of the structures of five untrained sequences, as well as the identification of the predominant conformations including G4, iM, and DS formed by two complementary G-rich and C-rich sequences in acidic and neutral pH conditions. The results of this study demonstrated the potential of the proposed methodology for rapid screening and prediction of secondary DNA conformations.

Energy–dependent femtosecond LIPSS on germanium and application in explosives sensing

Abstract In this study, we fabricated laser-induced periodic surface structures (LIPSS) on a germanium surface through laser ablation in air using axicon and femtosecond (fs) pulses. This novel approach permitted the nanoscale material processing outcome refinement via an fs Bessel beam. Our investigations aimed at systematically understanding the formation of periodic structures under various experimental conditions, such as (i) different pulse energies ranging from 50 µJ to 1000 µJ at a constant scan speed and (ii) constant energy with different scan speeds (0.1–3 mm s−1). By adjusting the fluences and scan speeds, we were able to identify the parametric space and alter the periodicity of the low-spatial frequency LIPSS and high-spatial frequency LIPSS on germanium, which were analyzed using field emission scanning electron microscopy. An optimal LIPSS formation over a large area of germanium was achieved at an input energy of 250 µJ and a scan speed of 0.75 mm s−1. Additionally, we measured the contact angles of the Ge nanostructures (GeNSs) to demonstrate their hydrophobic nature and non-wetting properties, providing insights into the behavior of LIPSS. Subsequently, the GeNSs were coated with a ∼15 nm thick gold (Au) film using a thermal deposition method. Utilizing these, the surface-enhanced Raman spectroscopy (SERS) technique detected diverse analytes, such as tetryl (an explosive) at a concentration of 50 µM and thiram (a pesticide) at 500 nM. The SERS enhancement factors for tetryl and thiram molecules on GeNSs coated with a 15 nm-thick Au layer were determined to be 2.5 × 104 and 4.2 × 105, respectively.

EDIG-CHANGE. III. The lagging eDIG revealed by multi-slit spectroscopy of NGC 891

The kinematic information of the extraplanar diffuse ionized gas (eDIG) around galaxies provides clues to the origin of the gas. The eDIG-CHANGES project studies the physical and kinematic properties of the eDIG around the CHANG-ES sample of nearby edge-on disk galaxies. We use a novel multi-slit narrow-band spectroscopy technique to obtain the spatial distribution of the spectral properties of the ionized gas around NGC 891, which is often regarded as an analogue of the Milky Way. We developed specific data reduction procedures for the multi-slit narrow-band spectroscopy data taken with the MDM 2.4m telescope. The data presented in this paper cover the Halpha and N II emission lines. The eDIG traced by the Halpha and N II lines shows an obvious asymmetric morphology, being brighter in the northeastern part of the galactic disk and extending a few kiloparsecs above and below the disk. Global variations in the N II /Halpha line ratio suggest additional heating mechanisms for the eDIG at large heights beyond photoionization. We also construct position-velocity (PV) diagrams of the eDIG based on our optical multi-slit spectroscopy data and compare them to similar PV diagrams constructed with the H I data. The dynamics of the two gas phases are generally consistent with each other. Modelling the rotation curves at different heights from the galactic mid-plane suggests a vertical negative gradient in turnover radius and maximum rotation velocity, with magnitudes of approximately $3 kpc kpc^ $ and $22-25 km s^ kpc^ $, respectively. Our measured vertical gradients of the rotation curve parameters suggest significant differential rotation of the ionized gas in the halo, often referred to as the lagging eDIG. Systematic study of the lagging eDIG, using the multi-slit narrow-band spectroscopy technique developed in our eDIG-CHANGES project, will help us to better understand the dynamics of the ionized gas in the halo.

Spectroscopic analysis of single and multiphase electrical discharge for clean energy conversion

Abstract In this study, we examined non-thermal atmospheric pressure plasma processes operating under varying conditions using different liquid and gaseous hydrocarbon materials. The light emission from the discharges were analyzed through optical emission spectroscopy to comprehend the products generated in different parameter space. The gaseous products from each of these analyses were also collected and analyzed through gas chromatography. Analysis of the optical emission from the discharge and concentration of the gaseous products show a linear trend between emission intensity ratio Hα/C2 and gas concentration ratio H2/C2Hx. Gas temperature and electronic excitation temperature of different experimental conditions were also compared and indicates that spark discharge relates to higher electronic excitation temperature compared to glow discharge of similar medium. Higher electronic excitation temperature leads to generation of different products from spark discharge compared to glow discharge. Glow discharge generates more of the intermediate products. Whereas spark discharge, because of its higher electronic excitation temperature, leads to higher rate of dissociation and therefore generates more of the dissociated products. Glow discharge, for example generates more of OH and H from the moisture present in the carrier gas as impurity, whereas spark discharge would generate more of Hα and O particles further breaking down the OH bonds. Finally, UV-Vis analysis was performed on the liquid products of the discharge and reveals that the photo-centers and the newly generated soot nano particles absorb the UV range lights and some of the visible range light emission mostly up to ~600nm.

Multiplexed SERS Detection of Serum Cardiac Markers Using Plasmonic Metasurfaces.

Surface-enhanced Raman spectroscopy (SERS) possesses exquisite molecular-specific properties with single-molecule sensitivity. Yet, translation of SERS into a quantitative analysis technique remains elusive owing to considerable fluctuation of the SERS intensity, which can be ascribed to the SERS uncertainty principle, a tradeoff between "reproducibility" and "enhancement". To provide a potential solution, herein, an integrated multiplexed SERS biosensing strategy is proposed, which features two distinct advantages. First, a subwavelength-structured plasmonic metasurface consisting of alternately stacked metal-dielectric pyramidal meta-atoms is fabricated and could provide simultaneously enhanced electric and magnetic fields to enable spatially extended and weakly wavelength-dependent SERS. Second, nanomechanical perturbations are harnessed to transduce signals in the form of SERS frequency shifts, which are not directly affected by the SERS uncertainty principle. By also employing 3D printing methods, a proof-of-concept study of multiplexed detection of a panel of serum cardiac biomarkers for acute myocardial infarction is provided. Success in the development of both the electric and magnetic fields-active plasmonic metasurfaces could transform future designs of SERS substrates with newly endowed functionalities, and frequency shift-based SERS multiplexing could open new opportunities to develop innovative quantitative optical techniques for applications in chemistry, biology, and medicine.

AN EX-VIVO SPECTRAL AND LIFETIME-DECAY ANALYSIS OF 5-ALA DERIVED PPIX flUORESCENCE: OBJECTIVE flUORESCENCE MAPPING IN GLIOMA SURGERY

Abstract AIMS 5ALA/Protoporphyrin IX (PpIX) fluorescence guided surgery (FGS) in high-grade glioma has been shown to increase resection and survival, despite this benefits are limited in low-grade glioma by low emission and subjective interpretation. Quantitative fluorescence could address these issues, however is challenging due to photobleaching and variations in tissue induced distortion and PpIX photochemical state that are poorly understood. Lifetime-decay measures intrinsic fluorophore properties and is not influenced by these factors, but is difficult to measure intra-operatively. We used paired optical and fluorescence spectroscopy with lifetime decay mapping to characterise PpIX emission within the glioma tissue microenvironment. METHOD Biopsies were collected from 20 patients undergoing glioma FGS, along with 4 controls from partial temporal lobectomies. Paired measurements of emission and lifetime were matched with optical property readings. Lifetime and emission ratios at 635 and 620nm were calculated (PpIX635/620), corresponding to the primary emission peak for the photochemical states of PpIX in tissue. Raw and optically corrected emission was correlated with lifetime decay. RESULTS 205 specimens were analysed by WHO grade (56 Grade4, 66 Grade3, 37 Grade2, 20 control). PpIX635/620 emission was 0.93 in control (CI 0.91-0.95), 1.03 in grade 2 tumours (CI 0.95-1.26), 1.56 in grade 3 (CI 1.22-1.91) and 6.99 (CI 5.78-8.20) in grade 4. PpIX635/620 lifetime correlated with emission (R2 =0.98, range 0.94-1.57). Correlation of emission with lifetime readings improved significantly following optical correction at 635nm (raw R2 =0.81, corrected R2 =0.90) and 620nm (raw R2 =0.44, corrected R2 =0.86). CONCLUSION PpIX620 and PpIX635 photochemical states are present in human glioma, with an increase in PpIX635/620 suggesting increased WHO grade. The ability to distinguish these forms holds the potential to provide real-time data for tumour differentiation and pathology. Accurate characterisation and correction of tissue induced distortion significantly improves the ability to detect, characterise and quantify PpIX intra-operatively.

Insights into the growth of GaN thin films through liquid gallium sputtering: A plasma-film combined analysis.

This study presents the detailed characterization of a magnetron-based Ar-N2 plasma discharge used to sputter a liquid Ga target for the deposition of gallium nitride (GaN) thin films. By utilizing in situ diagnostic techniques including optical emission spectroscopy and microwave interferometry, we determine different temperatures (rotational and vibrational of N2 molecules, and electronic excitation of Ar atoms) and electron density, respectively. Beyond providing insights into fundamental plasma physics, our research establishes a significant correlation between gas-phase dynamics, particularly those of gallium atoms (flux and average energy at the substrate) and deposited GaN thin film properties (growth rate and crystalline fraction). These findings underscore the role of plasma conditions in enhancing thin film quality, highlighting the importance of plasma characterization in understanding and optimizing GaN thin film growth processes.

Ultrafast spectroscopy of coherent phonons across the pressure driven insulator to metal phase transition in V2O3

Nowadays, materials science is moving towards the understanding and control of materials in nonequilibrium states by making use of perturbative techniques to investigate their dynamical responses. From this perspective, the use of ultrashort light pulses seems to be a relevant approach as it can selectively address different degrees of freedom in solid-state systems and more particularly electrons. Such a method can help to decipher the physical phenomena arising from electronic correlations and complements a more conventional methodology where the phase diagrams of materials are investigated at thermodynamical equilibrium. Here, we combine femtosecond optical spectroscopy and a high-pressure setup to monitor the ultrafast out-of-equilibrium photo response of a V2O3 thin film across the pressure driven insulator-to-metal transition. The experimental results demonstrate the possibility to use the spectroscopy of coherent phonons as a thermodynamical phase marker in V2O3 thin films. In addition, the frequency behavior of the ultrafast coherent phonon mode (A1g character) seems to reflect the manifestation of a strong coupling between the lattice and electronic degrees of freedom near first-order transition lines with a pronounced drop in frequency around the critical pressure. Published by the American Physical Society 2024

Impact of Surface Enhanced Raman Spectroscopy in Catalysis.

Catalysis stands as an indispensable cornerstone of modern society, underpinning the production of over 80% of manufactured goods and driving over 90% of industrial chemical processes. As the demand for more efficient and sustainable processes grows, better catalysts are needed. Understanding the working principles of catalysts is key, and over the last 50 years, surface-enhanced Raman Spectroscopy (SERS) has become essential. Discovered in 1974, SERS has evolved into a mature and powerful analytical tool, transforming the way in which we detect molecules across disciplines. In catalysis, SERS has enabled insights into dynamic surface phenomena, facilitating the monitoring of the catalyst structure, adsorbate interactions, and reaction kinetics at very high spatial and temporal resolutions. This review explores the achievements as well as the future potential of SERS in the field of catalysis and energy conversion, thereby highlighting its role in advancing these critical areas of research.

Initial evaluation of waste phosphogypsum for its use as a precursor for bioceramic materials

In this study, the phosphogypsum waste taken from various places in the factory dump located in Kėdainiai (Lithuania) was reinspected and characterised by different physico-chemical characterisation methods. The results of X-ray diffraction analysis, thermogravimetric analysis and differential scanning calorimetry, Fourier transform infrared spectroscopy, energy-dispersive X-ray analysis, elemental analysis using inductively coupled plasma optical emission and X-ray fluorescence spectroscopy confirmed that the main crystalline phase of the phosphogypsum waste is gypsum (CaSO4·2H2O). The surface morphology of the investigated materials was analysed using scanning electron microscopy. The specific surface area was determined by the Brunauer–Emmet–Teller method. The pore size distribution of the material produced was obtained using the Barrett–Joyner–Halenda method. This study also demonstrated that the phosphogypsum waste could be successfully used as a precursor for the dissolution-precipitation synthesis of high quality bioceramic calcium hydroxyapatite.

Optical spectroscopy of an excited Laughlin liquid

Neutral excitations with zero momentum in a Laughlin liquid at an electron filling factor of 1/3 have been studied. It was found that the lowest in energy are spin-magnetogravitons, excitations with a simultaneous change in the electron density in the Laughlin liquid and the spin quantum number of the electron system. The experimental possibility of the formation of new quasi-equilibrium states of anionic matter – Laughlin solutions of spin-magnetogravitons – is demonstrated. A new type of optical scattering is observed in Laughlin solutions.

Reconfigurable Antireflection Coatings Enabled by PDMS Oligomer Infusion in Templated Nanoporous Polymer Films.

The diffusion of uncured polydimethylsiloxane (PDMS) oligomers out of bulk PDMS elastomers is usually detrimental to many biomedical and microfluidic applications due to the inevitable contamination of the contacting fluids and substrates. Here, we transform this detrimental process into an enabling technology for achieving novel reconfigurable antireflection (AR) coatings, which are of great technological importance in the development of new nano-optical and optoelectronic applications. Self-assembled monolayer silica colloidal crystals are first used as sacrificial templates in fabricating nanoporous polymer AR coatings. When air in the templated nanopores is replaced with infused PDMS oligomers simply by pressing a PDMS stamp on a nanoporous AR film, the original antireflection conditions are lost, and the coating transforms from a low-reflection configuration to a high-reflection state. The original antireflection performance can be fully recovered by dissolving the infused oligomers in the appropriate solvents (e.g., hexane). This novel tuning mechanism for achieving reconfigurable AR properties has been confirmed by systematic investigations using various microscopes, optical spectroscopy, nanoindentation, thermomechanical tests, and X-ray photoelectron spectroscopy. Complex micropatterns with micrometer-scale spatial resolution and drastically different AR performances can be easily printed on nanoporous AR films by using a soft lithography-based microcontact printing process. Numerical finite-difference time-domain simulations match well with experimental antireflection measurements and reveal a linear relationship between the optical transmission and the amount of infused PDMS oligomers in nanopores.

Human health risk assessment of potentially toxic and essential elements in medicinal plants consumed in Zabol, Iran, using the Monte Carlo simulation method

Medicinal plants (MPs) have long been used for their therapeutic properties in traditional forms of medicine. However, the presence of potentially toxic elements (PTEs) in MPs raises concerns about their safety, efficacy, and potential adverse effects on human health. The current study aimed to determine the level of potentially toxic and essential elements (PTEEs) in commonly consumed MPs in Zabol, Iran, along with their health risk assessments. To conduct the present study, 10 types of MPs widely used in Zabol, Iran, were selected, and 15 samples of each type (150 samples in total) were taken. Each sample was analyzed for the presence of various PTEEs using Inductively Coupled Plasma Optical Emission Spectroscopy (ICP-OES) for Lead (Pb), cadmium (Cd), chrome (Cr), nickel (Ni), copper (Cu), zinc (Zn), iron (Fe), aluminum (Al) and manganese (Mn); and Atomic Absorption Spectrometry (AAS) for arsenic (As) and mercury (Hg). Finally, to better comprehend the scope of exposure and its possible effects, the Monte Carlo simulation method is successfully applied to assess human health risks related to PTEs in MPs. Statistical analysis revealed statistically significant (P < 0.001) variations in PTE averages among MP types. Furthermore, all samples’ overall PTE mean concentration (range: 0.18 to 215.5 µg/kg) was below the World Health Organization’s (WHO) regulatory standards. Probabilistic health risks, including non-carcinogenic-target hazard quotient (THQ) for each element, total target hazard quotient (TTHQ) for all elements, and carcinogenic-incremental lifetime cancer risk (ILCR) for each element, and total carcinogenic risk (TCR) for all elements, were significantly lower than the acceptable limit for children and adults. Accordingly, it can be said that consuming MPs sold in Zabol is safe for children and adults regarding carcinogenic (ILCR/TCR = 10− 4) and non-carcinogenic (THQ/TTHQ = 1) effects. In light of the findings presented here, and to our understanding, the primary factor contributing to lower levels of PTEs in MPs in Zabol City markets is the cultivation of plants in nonindustrialized areas, separate from urban and industrial zones. This practice keeps them from environmental contaminations, including soil quality and water sources. It is recommended that it is essential to regulate the sources that enhance the transfer of PTEs and other harmful pollutants from surroundings to the soil and, consequently, MPs. It is also suggested that, like chemical drugs, MPs should undergo rigorous testing by quality control agencies before being made available to the market.

Study of Neural Network Architectures for Determining Gas Concentrations by Spectra

A study of a number of neural networks of different architectures for determining gas concentrations from spectra obtained using an optical emission gas analyzer, which measures the spectrum of electromagnetic radiation emitted by gases when excited by an electric discharge, is presented. The neural network is trained on data from the optical spectroscopy laboratory and is able to predict gas concentrations from spectra at high speed. The research concerned the deep neural network architectures with convolutional and recurrent layers. Convolutional layers highlight the features of the spectra, while recurrent layers take into account the consistent structure of the data. The quality of the neural network is evaluated by the R2 coefficient of determination, and the comparison between networks by the RMSE indicator between the predicted and real gas concentrations.

Rapid diagnosis and recurrence prediction of choledocholithiasis disease using raw bile with machine learning assisted SERS

Surface-enhanced Raman spectroscopy (SERS) analysis based on body fluids has been widely applied in disease diagnose. Choledocholithiasis is a widespread and often recurrent digestive system disease, with limited data on factors predicting its formation and reappearance. Bile contains many components that could provide valuable diagnostic information; however, the current diagnosis of biliary disease by SERS focuses on detecting specific component in the bile, overlooking the complex interplay and correlations among multiple factors that could be crucial for accurate diagnosis. This work directly obtained multi-component SERS spectral information of raw bile from 46 patients. Characteristic information was extracted from bile SERS spectra using Principal Component Analysis (PCA), revealing variations in the content of characteristic components associated with different choledocholithiasis types and their recurrence frequency. Pearson correlation analysis was also introduced to reveal the interactions of primary active substances pertinent to choledocholithiasis diagnosis. The efficacy of PCA and Support Vector Machine (SVM) models in classifying stone types, presented an accuracy of 99.2 %. Furthermore, the interaction patterns among SERS characteristic components in choledocholithiasis recurrence frequency were revealed, and with the support of SVM, the prediction for different recurrence rates reached an accuracy of 95.2 %. Overall, this work demonstrates that integrating SERS with machine learning can support disease diagnosis and the interpretation of correlations among multiple components, facilitating elucidating the disease mechanisms.

Fast On-Site Speciation and High Spatial Resolution Imaging of Labile Arsenic in Freshwater and Sediment Using the DGT-SERS Sensor.

Diffusive gradients in thin films (DGT) technique is renowned for in situ passive sampling but not for rapid on-site analysis, whereas surface-enhanced Raman spectroscopy (SERS) excels in ultrasensitive on-site detection but is limited by substrate contamination from complex matrices. Here, a hierarchical nanostructure of silver (Ag) mirror-supported large Ag nanoparticles (∼120 nm) was grown in situ in polyacrylamide hydrogel with a restricted pore size (PAM/Ag mirror/AgNPs) to serve as both the DGT binding phase and the SERS substrate. The substrate exhibited a maximum electric field enhancement factor of 9.9 × 108 and a signal relative standard error of 4.8%. Using the DGT-SERS sensor, As(III) and As(V) in freshwater were simultaneously detected at limits of 0.9 and 0.8 μg L-1, respectively, applicable across a wide range of environmental conditions. The DGT-SERS effectively mitigated the interfacial reduction of As(V) caused by humic acid by excluding it from plasmonic hotspots through size exclusion of the diffusive layer. The Raman analysis of a DGT sample in the field requires only 2 s using a portable spectrometer without DGT device disassembly. More importantly, the DGT-SERS captured the first two-dimensional image of As(III) and As(V) in one DGT at the micron scale resolution, revealing their spatially supplementary distribution patterns at the sediment-water interface. This study paves the way for next-generation speciation imaging DGT and the application of SERS in complex environments.

The Tula Industrial Area Field Experiment: Quantitative Measurements of Formaldehyde, Sulfur Dioxide, and Nitrogen Dioxide Emissions Using Mobile Differential Optical Absorption Spectroscopy Instruments

The Tula industrial area in Central Mexico comprises, among other industries, a refinery and a thermoelectric power plant. It is well known for its constant emissions of gases into the atmosphere and considered an important area where pollutants released into the atmosphere have an influence on local and regional air quality. During March and April 2017, a field campaign was conducted with the objective of quantifying formaldehyde (HCHO), sulfur dioxide (SO2), and nitrogen dioxide (NO2) emissions from this industrial area using mobile differential optical absorption spectroscopy (DOAS) instruments. Calculated average emissions of the Francisco Perez Rios Power Plant and the Miguel Hidalgo Refinery were 3.14 ± 2.13 tons per day of HCHO, 362.08 ± 300.14 tons per day of SO2, and 24.76 ± 12.82 tons per day of NO2. From the measurements conducted, the spatial distribution patterns of SO2, NO2, and HCHO were reconstructed, showing a dispersion pattern of SO2 and NO2 towards the southwest of the industrial complex, impacting agricultural and urban areas. Occasionally, and usually during the morning hours, SO2 and NO2 were dispersed towards the north or northeast of the industrial complex. In the case of HCHO, dispersion was observed towards the south and southeast of the industrial complex. The far-reaching implications of this study are that for the first time, formaldehyde emissions were quantified. In addition, a follow-up study was conducted regarding nitrogen dioxide and sulfur dioxide emissions from the Tula Industrial area.