Cavity-enhanced Raman Spectroscopy Research Articles

Monitoring of gas composition in a laboratory biogas plant using cavity enhanced Raman spectroscopy.

Biogas production from organic raw materials is a highly complex biotechnological process. The responsible anaerobic fermentation process is difficult to measure due to its multi-stage nature. Still, optimization of biogas production and the development of robust and efficient process management strategies require continually updated information about the process. Hence, the development of a comprehensive sensor system with high temporal resolution is key to further advancement in biogas technology. Here, we demonstrate a gas sensor based on cavity enhanced Raman spectroscopy for biogas monitoring. Online detection of all gas components of a biogas mixture enables a comprehensive quantification. In addition, robust calibration routines facilitate the adaptation of the sensor for biogas monitoring. A simulated concentration course of a typical fermentation process with defined gas mixtures consisting of CH4, CO2, N2, O2 and H2 showed reliable results for all relevant biogas components for varying concentration ranges from ppm to 100 vol%. The response time of 5 seconds allows online detection and - as a consequence - real time information is obtained about the biogas composition. A laboratory biogas reactor was designed to operate biogas production on a miniaturized scale and analyze it using the Raman gas sensor. The developed sensor enables the observation of methane production throughout the first 24 h of the fermentation process. The obtained results show the suitability of cavity enhanced Raman spectroscopy as a gas sensor to monitor the entire process of biogas production. As this strategy would allow the process to be manipulated and optimized according to the current state, it is of great biotechnological interest.

注入锁定腔增强拉曼光谱微量气体检测技术

注入锁定腔增强拉曼光谱微量气体检测技术

Repartitioning of glycerol between levitated and surrounding deposited glycerol/NaNO3/H2O droplets.

Repartitioning of semi-volatile organic compounds (SVOCs) between particles is an important process to understand the particle growth and shrinkage in the atmosphere environment. Here, by using optical tweezers coupled with cavity-enhanced Raman spectroscopy, we report the repartitioning of glycerol between a levitated glycerol/NaNO3/H2O droplet and surrounding glycerol/NaNO3/H2O droplets deposited on the inner wall of a chamber with different organic to inorganic molar ratios (OIRs). For the high OIR with 3 : 1, no NaNO3 crystallization occurs both for levitated and deposited droplets in the whole relative humidity (RH) range, the radius of the levitated droplet decreases slowly due to the evaporation of glycerol from the levitated droplet at constant RHs. The levitated droplets radii with OIR of 1 : 1 and 1 : 3 increase with constant RHs that are lower than 45.3% and 55.7%, respectively, indicating that the repartitioning of glycerol occurs. The reason is that NaNO3 in the deposited droplets is crystallized when RH is lower than 45.3% for 1 : 1 or 55.7% for 1 : 3. So the vapour pressure of glycerol at the surface of deposited droplets is higher than that of the levitated droplet which always remains as liquid droplet without NaNO3 crystallization, resulting in the transfer of glycerol from the deposited ones to the levitated one. The process of the glycerol repartitioning we discussed herein is a useful model to interpret the repartitioning of SVOCs between the externally mixed particles with different phase states.

A Direct Bicarbonate Detection Method Based on a Near-Concentric Cavity-Enhanced Raman Spectroscopy System.

Raman spectroscopy has great potential as a tool in a variety of hydrothermal science applications. However, its low sensitivity has limited its use in common sea areas. In this paper, we develop a near-concentric cavity-enhanced Raman spectroscopy system to directly detect bicarbonate in seawater for the first time. With the aid of this near-concentric cavity-enhanced Raman spectroscopy system, a significant enhancement in HCO3− detection has been achieved. The obtained limit of detection (LOD) is determined to be 0.37 mmol/L—much lower than the typical concentration of HCO3− in seawater. By introducing a specially developed data processing scheme, the weak HCO3− signal is extracted from the strong sulfate signal background, hence a quantitative analysis with R2 of 0.951 is made possible. Based on the spectra taken from deep sea seawater sampling, the concentration of HCO3− has been determined to be 1.91 mmol/L, with a relative error of 2.1% from the reported value (1.95 mmol/L) of seawater in the ocean. It is expected that the near-concentric cavity-enhanced Raman spectroscopy system could be developed and used for in-situ ocean observation in the near future.

Initial Collision Process of Two Miscible Droplets.

Dynamic properties of the metastable interface between two miscible solutions are investigated by the collision of two droplets. A clear interface is observed between the two colliding droplets. The interface moves in the colliding droplet toward the side where the original droplet has a lower surface tension. The interface is set to the middle of the colliding droplet by controlling the surface tension of the droplets to observe the chemical reactions at the droplet interface by cavity-enhanced Raman spectroscopy. This study provides a foundation for further research on the initial process of the chemical reactions of two miscible solutions.

Evaporation and Subsequent Adsorption of Alcohol Molecules at Aqueous Droplet Surface Observed by Cavity-Enhanced Raman Spectroscopy.

Mass transfer toward and across liquid surfaces is important for the interpretation of various interfacial phenomena, such as evaporation, adsorption, and mass accommodation, which have been investigated by the use of various methods. These studies, however, have focused on only one of the mass-transfer processes occurring at the surface. We investigate the surface concentration of alcohol molecules at aqueous droplet surfaces on the several-millisecond time scale using cavity-enhanced droplet Raman spectroscopy. A decrease and subsequent increase of the alcohol concentration are observed in a set of measurements, which arise from an evaporation and subsequent adsorption of the alcohol molecules at the surface. This facilitates an understanding of the surface kinetics of molecules at the liquid surfaces.

Cavity-Enhanced Raman Spectroscopy in the Biosciences: In Situ, Multicomponent, and Isotope Selective Gas Measurements To Study Hydrogen Production and Consumption by Escherichia coli.

Recently we introduced cavity-enhanced Raman spectroscopy (CERS) with optical feedback cw-diode lasers as a sensitive analytical tool. Here we report improvements made on the technique and its first application in the biosciences for in situ, multicomponent, and isotope selective gas measurements to study hydrogen production and consumption by Escherichia coli. Under anaerobic conditions, cultures grown on rich media supplemented with d-glucose or glycerol produce H2 and simultaneously consume some of it. By introducing D2 in the headspace, hydrogen production and consumption could be separated due to the distinct spectroscopic signatures of isotopomers. Different phases with distinctly different kinetic regimes of H2 and CO2 production and D2 consumption were identified. Some of the D2 consumed is converted back to H2 via H/D exchange with the solvent. HD was formed only as a minor component. This reflects either that H/D exchange at hydrogenase active sites is rapid compared to the rate of recombination, rapid recapture of HD occurs after the molecule is formed, or that the active sites where D2 oxidation and proton reduction occur are physically separated. Whereas in glucose supplemented cultures, addition of D2 led to an increase in H2 produced, while the yield of CO2 remained unchanged; with glycerol, addition of D2 led not only to increased yields of H2, but also significantly increased CO2 production, reflecting an impact on fermentation pathways. Addition of CO was found to completely inhibit H2 production and significantly reduce D2 oxidation, indicating at least some role for O2-tolerant Hyd-1 in D2 consumption.

Cavity-Enhanced Raman Spectroscopy of Natural Gas with Optical Feedback cw-Diode Lasers.

We report on improvements made on our previously introduced technique of cavity-enhanced Raman spectroscopy (CERS) with optical feedback cw-diode lasers in the gas phase, including a new mode-matching procedure which keeps the laser in resonance with the optical cavity without inducing long-term frequency shifts of the laser, and using a new CCD camera with improved noise performance. With 10 mW of 636.2 nm diode laser excitation and 30 s integration time, cavity enhancement achieves noise-equivalent detection limits below 1 mbar at 1 bar total pressure, depending on Raman cross sections. Detection limits can be easily improved using higher power diodes. We further demonstrate a relevant analytical application of CERS, the multicomponent analysis of natural gas samples. Several spectroscopic features have been identified and characterized. CERS with low power diode lasers is suitable for online monitoring of natural gas mixtures with sensitivity and spectroscopic selectivity, including monitoring H2, H2S, N2, CO2, and alkanes.

Liquid–Liquid Phase Separation in Mixed Organic/Inorganic Single Aqueous Aerosol Droplets

Direct measurements of the phase separation relative humidity (RH) and morphology of aerosol particles consisting of liquid organic and aqueous inorganic domains are presented. Single droplets of mixed phase composition are captured in a gradient force optical trap, and the evolving size, refractive index (RI), and morphology are characterized by cavity-enhanced Raman spectroscopy. Starting at a RH above the phase separation RH, the trapped particle is dried to lower RH and the transition to a phase-separated structure is inferred from distinct changes in the spectroscopic fingerprint. In particular, the phase separation RHs of droplets composed of aqueous solutions of polyethylene glycol (PEG-400)/ammonium sulfate and a mixture of C6-diacids/ammonium sulfate are probed, inferring the RH from the RI of the droplet immediately prior to phase separation. The observed phase separation RHs occur at RH marginally higher (at most 4%) than reported in previous measurements made from studies of particles deposited on hydrophobic surfaces by brightfield imaging. Clear evidence for the formation of phase-separated droplets of core-shell morphology is observed, although partially engulfed structures can also be inferred to form. Transitions between the different spectroscopic signatures of phase separation suggest that fluctuations in morphology can occur. For droplets that are repeatedly cycled through the phase separation RH, the water activity at phase separation is found to be remarkably reproducible (within ±0.0013) and is the same for the 1-phase to 2-phase transition and the 2-phase to 1-phase transition. By contrast, larger variation between the water activities at phase separation is observed for different droplets (typically ±0.02).

Toward optical-tweezers-based force microscopy for airborne microparticles.

Optical tweezers have found widespread application in biological and colloidal physics for the measurement of pN forces over nanometer to micrometer length scales. Similar aerosol-phase measurements of interparticle force have not been reported in spite of the potential to better resolve particle coagulation kinetics. Various refractive index mismatches in the beam path as well as the need to explicitly account for gravity and inertial particle motion provide a number of challenges that must be overcome to make such measurements tractable. In this regard, we demonstrate schemes by which the particle position and trap stiffness may be unambiguously measured using bright-field microscopy with resolution comparable with analogous condensed-phase measurements. Moreover, some of the challenges of working with highly dynamic aqueous particles are introduced and exploited to observe size-dependent phenomena in aerosol optical tweezers. Notably, when combined with cavity-enhanced Raman spectroscopy, this provides a unique opportunity to explore trapping forces over a continuum of particle size and refractive index. It is expected that the methods developed will provide a basis for the measurement of pairwise interaction forces in aerosol optical tweezers while providing a probe of fundamental airborne particle trapping dynamics.

Reversible control of the equilibrium size of a single aerosol droplet by change in relative humidity.

Noncontact levitation of single micrometer-sized water droplets in air can be achieved by a laser trapping technique. The equilibrium size of a water droplet is quite sensitive to relative humidity in the surrounding gas phase. In order to investigate the physical and chemical properties of single water droplets in air as a function of the droplet size or solute concentration, laser trapping experiments were conducted under controlled humidity conditions. In this study, we developed a trapping chamber equipped with a relative humidity controller and demonstrated the reversible control of the equilibrium size of a single droplet levitated in air through a change in relative humidity. Furthermore, relative humidity was successfully evaluated by means of cavity enhanced Raman spectroscopy of a trapped water droplet.

Volatility and oxidative aging of aqueous maleic acid aerosol droplets and the dependence on relative humidity.

The microphysical structure and heterogeneous oxidation by ozone of single aerosol particles containing maleic acid (MA) has been studied using aerosol optical tweezers and cavity enhanced Raman spectroscopy. The evaporation rate of MA from aqueous droplets has been measured over a range of relative humidities and the pure component vapor pressure determined to be (1.7 ± 0.2) × 10(-3) Pa. Variation in the refractive index (RI) of an aqueous MA droplet with relative humidity (RH) allowed the subcooled liquid RI of MA to be estimated as 1.481 ± 0.001. Measurements of the hygroscopic growth are shown to be consistent with equilibrium model predictions from previous studies. Simultaneous measurements of the droplet composition, size, and refractive index have been made during ozonolysis at RHs in the range 50-80%, providing insight into the volatility of organic products, changes in the droplet hygroscopicity, and optical properties. Exposure of the aqueous droplets to ozone leads to the formation of products with a wide range of volatilities spanning from involatile to volatile. Reactive uptake coefficients show a weak dependence on ozone concentration, but no dependence on RH or salt concentration. The time evolving RI depends significantly on the RH at which the oxidation proceeds and can even show opposing trends; while the RI increases with ozone exposure at low relative humidity, the RI decreases when the oxidation proceeds at high relative humidity. The variations in RI are broadly consistent with a framework for predicting RIs for organic components published by Cappa et al. ( J. Geophys. Res. 2011 , 116 , D15204 ). Once oxidized, particles are shown to form amorphous phases on drying rather than crystallization, with slow evaporation kinetics of residual water.

Enhanced Raman multigas sensing – a novel tool for control and analysis of13CO2labeling experiments in environmental research

Cavity-enhanced Raman multigas spectrometry is introduced as a versatile technique for monitoring of (13)CO2 isotope labeling experiments, while simultaneously quantifying the fluxes of O2 and other relevant gases across a wide range of concentrations. The multigas analysis was performed in a closed cycle; no gas was consumed, and the gas composition was not altered by the measurement. Isotope labeling of plant metabolites via photosynthetic uptake of (13)CO2 enables the investigation of resource flows in plants and is now an important tool in ecophysiological studies. In this experiment the (13)C labeling of monoclonal cuttings of Populus trichocarpa was undertaken. The high time resolution of the online multigas analysis allowed precise control of the pulse labeling and was exploited to calculate the kinetics of photosynthetic (13)CO2 uptake and to extrapolate the exact value of the (13)CO2 peak concentration in the labeling chamber. Further, the leaf dark respiration of immature and mature leaves was analyzed. The quantification of the photosynthetic O2 production rate as a byproduct of the (13)CO2 uptake correlated with the amount of available light and the leaf area of the plants in the labeling chamber. The ability to acquire CO2 and O2 respiration rates simultaneously also simplifies the determination of respiratory quotients (rate of O2 uptake compared to CO2 release) and thus indicates the type of combusted substrate. By combining quantification of respiration quotients with the tracing of (13)C in plants, cavity enhanced Raman spectroscopy adds a valuable new tool for studies of metabolism at the organismal to ecosystem scale.

Strong Enhancement of Light–Matter Interaction in Graphene Coupled to a Photonic Crystal Nanocavity

We demonstrate a large enhancement in the interaction of light with graphene through coupling with localized modes in a photonic crystal nanocavity. Spectroscopic studies show that a single atomic layer of graphene reduces the cavity reflection by more than a factor of one hundred, while also sharply reducing the cavity quality factor. The strong interaction allows for cavity-enhanced Raman spectroscopy on subwavelength regions of a graphene sample. A coupled-mode theory model matches experimental observations and indicates significantly increased light absorption in the graphene layer. The coupled graphene-cavity system also enables precise measurements of graphene's complex refractive index.

Phase, Morphology, and Hygroscopicity of Mixed Oleic Acid/Sodium Chloride/Water Aerosol Particles before and after Ozonolysis

Aerosol optical tweezers are used to probe the phase, morphology, and hygroscopicity of single aerosol particles consisting of an inorganic component, sodium chloride, and a water insoluble organic component, oleic acid. Coagulation of oleic acid aerosol with an optically trapped aqueous sodium chloride droplet leads to formation of a phase-separated particle with two partially engulfed liquid phases. The dependence of the phase and morphology of the trapped particle with variation in relative humidity (RH) is investigated by cavity enhanced Raman spectroscopy over the RH range <5% to >95%. The efflorescence and deliquescence behavior of the inorganic component is shown to be unaffected by the presence of the organic phase. Whereas efflorescence occurs promptly (<1 s), the deliquescence process requires both dissolution of the inorganic component and the adoption of an equilibrium morphology for the resulting two phase particle, occurring on a time-scale of <20 s. Comparative measurements of the hygroscopicity of mixed aqueous sodium chloride/oleic acid droplets with undoped aqueous sodium chloride droplets show that the oleic acid does not impact on the equilibration partitioning of water between the inorganic component and the gas phase or the time response of evaporation/condensation. The oxidative aging of the particles through reaction with ozone is shown to increase the hygroscopicity of the organic component.

Cavity-enhanced Raman spectroscopy with optical feedback cw diode lasers for gas phase analysis and spectroscopy

A variant of cavity-enhanced Raman spectroscopy (CERS) is introduced, in which diode laser radiation at 635 nm is coupled into an external linear optical cavity composed of two highly reflective mirrors. Using optical feedback stabilisation, build-up of circulating laser power by 3 orders of magnitude occurs. Strong Raman signals are collected in forward scattering geometry. Gas phase CERS spectra of H(2), air, CH(4) and benzene are recorded to demonstrate the potential for analytical applications and fundamental molecular studies. Noise equivalent limits of detection in the ppm by volume range (1 bar sample) can be achieved with excellent linearity with a 10 mW excitation laser, with sensitivity increasing with laser power and integration time. The apparatus can be operated with battery powered components and can thus be very compact and portable. Possible applications include safety monitoring of hydrogen gas levels, isotope tracer studies (e.g., (14)N/(15)N ratios), observing isotopomers of hydrogen (e.g., radioactive tritium), and simultaneous multi-component gas analysis. CERS has the potential to become a standard method for sensitive gas phase Raman spectroscopy.

Towards an integrated optical single aerosol particle lab

We present a manipulation and characterization system for single airborne particles which is integrated onto a microscope slide. Trapped particles are manipulated by means of radiation pressure and characterized by cavity enhanced Raman spectroscopy. Optical fibers are used to deliver the trapping laser light as well as to collect the Raman scattered light, allowing for a flexible usage of the device. The system features a sample chamber which is separated from an aerosol-flooded injection chamber by means of a light guiding glass-capillary. The coupling of this device with an aerosol optical tweezers setup to selectively load its trapping sites is demonstrated. Finally, a route towards chip-integrated handling and processing of multiple particles is shown and the first results are presented.

Observation of bistability of trapping position in aerosol optical tweezers

Bistability in the axial trapping position of aqueous aerosol droplets has been observed for the first time, to our knowledge, in optical tweezers. The behavior has been observed for two distinct trapping configurations, with the trapping beam oriented either along the vertical or horizontal axis. This represents the first report of the optical tweezing of aerosol droplets with a horizontally propagating laser beam. Side imaging was used in conjunction with imaging in the plane of the optical trap. Droplet sizing was performed using cavity-enhanced Raman spectroscopy or by applying a circular regression routine to the acquired images. Predictions from a theoretical model of optical forces are shown to be in good agreement with the experimental observations of bistability in the trapping position. These studies have significance both for the rigorous interpretation of data obtained using aerosol optical tweezers and for the modeling of aerosol optical traps.

Radius measurements of optically trapped aerosols through Brownian motion

Optical trapping of liquid aerosols from polydisperse samples provides unique problems for measuring their radii. Perhaps the most precise method, cavity-enhanced Raman spectroscopy (CERS), is limited to relatively large aerosols (>2 μm in radius). Determining particle perimeters in video microscopy lacks precision and, although simple, can be ambiguous. Here we demonstrate a simple and precise method based on studying the Brownian motion of droplets as they approach a nearby surface. We obtain results with greater precision and reliability than video microscopy, and with no size limitation conclude the technique could compete with CERS in terms of precision and accuracy.

Spectroscopic characterisation and manipulation of arrays of sub-picolitre aerosol droplets

Arrays of optically tweezed aerosol droplets, each of sub-picolitre volume, are manipulated by holographic optical tweezers and characterised by cavity enhanced Raman spectroscopy. A spatial light modulator is employed to generate arrays of optical traps from a single laser beam and to control the array dimensions and relative trap positions. Comparative hygroscopicity measurements are performed concurrently on five trapped droplets by monitoring the evolving size of each droplet. This is extended to the controlled coalescence of an array of droplets accompanied by spectroscopic measurements. These data represent the first ever simultaneous measurements of the evolving composition and size of an array of aerosol droplets. We consider the possibility of using aerosol arrays as a platform for studying chemical reactions in sub-picolitre volumes, exploiting the versatility of aerosol arrays for performing optical digital microfluidic operations accompanied by micro-total analysis.