Open-Path Laser Absorption Sensor for Mobile Measurements of Atmospheric Ammonia.

Anthropogenic emissions of ammonia to the atmosphere, particularly those from agricultural sources, can be damaging to the environment and human health and can drive a need for sensor technologies that can be used to detect and quantify the emissions. Mobile sensing approaches that can be deployed on ground-based or aerial vehicles can provide scalable solutions for high throughput measurements but require relatively compact and low-power sensor systems. This contribution presents an ammonia sensor based on wavelength modulation spectroscopy (WMS) integrated with a Herriott multi-pass cell and a quantum cascade laser (QCL) at 10.33 µm oriented to mobile use. An open-path configuration is used to mitigate sticky-gas effects and achieve high time-response. The final sensor package is relatively small (~20 L), lightweight (~3.5 kg), battery-powered (<30 W) and operates autonomously. Details of the WMS setup and analysis method are presented along with laboratory tests showing sensor accuracy (<~2%) and precision (~4 ppb in 1 s). Initial field deployments on both ground vehicles and a fixed-wing unmanned aerial vehicle (UAV) are also presented.

Ozone Detection via Deep-Ultraviolet Cavity-Enhanced Absorption Spectroscopy with a Laser Driven Light Source.

We present a novel sensing approach for ambient ozone detection based on deep-ultraviolet (DUV) cavity-enhanced absorption spectroscopy (CEAS) using a laser driven light source (LDLS). The LDLS has broadband spectral output which, with filtering, provides illumination between ~230-280 nm. The lamp light is coupled to an optical cavity formed from a pair of high-reflectivity (R~0.99) mirrors to yield an effective path length of ~58 m. The CEAS signal is detected with a UV spectrometer at the cavity output and spectra are fitted to yield the ozone concentration. We find a good sensor accuracy of <~2% error and sensor precision of ~0.3 ppb (for measurement times of ~5 s). The small-volume (<~0.1 L) optical cavity is amenable to a fast response with a sensor (10-90%) response time of ~0.5 s. Demonstrative sampling of outdoor air is also shown with favorable agreement against a reference analyzer. The DUV-CEAS sensor compares favorably against other ozone detection instruments and may be particularly useful for ground-level sampling including that from mobile platforms. The sensor development work presented here can also inform of the possibilities of DUV-CEAS with LDLSs for the detection of other ambient species including volatile organic compounds.

In-Situ Elemental Composition Analysis of Large Inhalable Aerosol Using Laser Induced Breakdown Spectroscopy.

The ability to obtain information on the composition of airborne particles is a necessary part of identifying and controlling risks from exposure to potentially toxic materials, especially in the workplace. However, very few aerosol sampling instruments can characterize elemental composition in real time or measure large inhalable particles with aerodynamic diameter exceeding 20 µm. Here, we present the development and validation of a method for real time elemental composition analysis of large inhalable particles using laser-induced breakdown spectroscopy (LIBS). The prototype sensor uses a passive inlet and an optical triggering system to ablate falling particles with an LIBS plasma. Particle composition is quantified based on collected emission spectra using a real-time material classification algorithm. The approach was validated with a set of 1480 experimental spectra from four different aerosol test materials. We have studied effects of varying detection thresholds and find operating conditions with good agreement to truth values (F1 score ≥ 0.9). Details of the analysis method, including subtracting the spectral contribution from the air plasma and reasons for the infrequent misclassifications, are discussed. The LIBS elemental analysis can be combined with our previously demonstrated direct-reading particle sizer (DRPS) to provide a system capable of both counting, sizing, and elemental analysis of large inhalable particles.

Mobile Measurement System for the Rapid and Cost-Effective Surveillance of Methane and Volatile Organic Compound Emissions from Oil and Gas Production Sites.

In this study, a ground-based mobile measurement system was developed to provide rapid and cost-effective emission surveillance of both methane (CH4) and volatile organic compounds (VOCs) from oil and gas (O&G) production sites. After testing in several controlled release experiments, the system was deployed in a field campaign in the Eagle Ford basin, TX. We found fat-tail distributions for both methane and total VOC (C4-C12) emissions (e.g., the top 20% sites ranked according to methane and total VOC (C4-C12) emissions were responsible for ∼60 and ∼80% of total emissions, respectively) and a good correlation between them (Spearman's R = 0.74). This result suggests that emission controls targeting relatively large emitters may help significantly reduce both methane and VOCs in oil and wet gas basins, such as the Eagle Ford. A strong correlation (Spearman's R = 0.84) was found between total VOC (C4-C12) emissions estimated using SUMMA canisters and data reported from a local ambient air monitoring station. This finding suggests that this system has the potential for rapid emission surveillance targeting relatively large emitters, which can help achieve emission reductions for both greenhouse gas (GHG) and air toxics from O&G production well pads in a cost-effective way.

Resonant dual-pulse laser ignition technique based on oxygen REMPI pre-ionization.

This contribution investigates a novel laser ignition method based on a dual-pulse resonant pre-ionization scheme. The first laser pulse efficiently creates initial gas ionization (seed electrons) through a 2 + 1 resonantly-enhanced multiphoton ionization (REMPI) scheme targeting molecular oxygen (λ ~ 287.6 nm). This pulse is followed by a second non-resonant near-infrared pulse (λ = 1064 nm) for energy addition into the gas via inverse bremsstrahlung absorption. The sequence of two pulses creates a laser induced plasma that exhibits high peak electron number density and temperature (ne ~ 8 × 1017 cm-3 at t = 100 ns and T ~ 8000 K at t = 10 µs, respectively). These plasma parameters are similar to those attained for typical single-pulse near-infrared laser plasmas but with the advantage of substantially lower pulse energy (by factor of ~ 2.5) in the dual-pulse REMPI case. A combustion study focusing on ignition of propane/air mixtures shows that the dual-pulse REMPI method leads to an extension of the lean flammability limit, and an increase in combustion efficiency near the lean limit, as compared to laser ignition with a single NIR pulse. The measurement results and observed gas dynamics are discussed in the context of their impact on combustion applications.

Gas dynamics and vorticity generation in laser-induced breakdown of air.

Research has shown that the ignition characteristics of laser-induced plasmas in fuel-air mixtures are influenced by the gas dynamics effects induced during the gas breakdown stage. Here, we present the numerical modeling of the fluid mechanics induced by breakdown (plasma formation) from a nanosecond near-infrared (NIR) laser pulse in air. The simulations focus on the post-discharge kernel dynamics with the goal of developing a better understanding of how vorticity is generated during the kernel cooling phase. Initial conditions (ICs) of kernel shape, temperature, and pressure (corresponding to the end of the laser pulse) are found from experimental Rayleigh scattering data. It is shown that this method for determining ICs is preferred versus the use of the Taylor-Sedov blast wave theory as it provides a more accurate description of the starting field. Past experimental observations have revealed that the gas dynamics of nanosecond laser sparks typically lead to the formation of an asymmetric torus with a frontal lobe propagating towards the laser source. We show that the development of the asymmetric torus is governed by strong vorticity generated through baroclinic torque arising from the blast wave that forms at the kernel boundary. Initially, the blast takes the shape of the teardrop kernel but then evolves into a spherical front during the first ∼10 µs because the blast wave strength varies along its circumference. This spatial variation leads to a misalignment between the pressure and density gradients and generation of vorticity by baroclinic torque. Ultimately, the observed flow-field is dictated by how the energy was initially deposited around the beam waist during breakdown. As such, one can tailor the aerodynamics induced during the cooling and recombination phase by controlling the energy deposition profile.

Cavity Ring-Down Methane Sensor for Small Unmanned Aerial Systems.

We present the development, integration, and testing of an open-path cavity ring-down spectroscopy (CRDS) methane sensor for deployment on small unmanned aerial systems (sUAS). The open-path configuration used here (without pump or flow-cell) enables a low mass (4 kg) and low power (12 W) instrument that can be readily integrated to sUAS, defined here as having all-up mass of <25 kg. The instrument uses a compact telecom style laser at 1651 nm (near-infrared) and a linear 2-mirror high-finesse cavity. We show test results of flying the sensor on a DJI Matrice 600 hexacopter sUAS. The high sensitivity of the CRDS method allows sensitive methane detection with a precision of ~10-30 ppb demonstrated for actual flight conditions. A controlled release setup, where known mass flows are delivered, was used to simulate point-source methane emissions. Examples of methane plume detection from flight tests suggest that isolated plumes from sources with a mass flow as low as ~0.005 g/s can be detected. The sUAS sensor should have utility for emissions monitoring and quantification from natural gas infrastructure. To the best of our knowledge, it is also the first CRDS sensor directly deployed onboard an sUAS.

Open-path cavity ring-down methane sensor for mobile monitoring of natural gas emissions.

We present the design, development, and testing results of a novel laser-based cavity ring-down spectroscopy (CRDS) sensor for methane detection. The sensor is specifically oriented for mobile (i.e. vehicle deployed) monitoring of natural gas emissions from oil and infrastructure. In contrast to most commercial CRDS sensors, we employ an open-path design which allows higher temporal response and a lower power and mass package more suited to vehicle integration. The system operates in the near-infrared (NIR) at 1651 nm with primarily telecom components and includes cellular communication for wireless data transfer. Along with basic sensor design and lab testing, we present results of field measurements showing performance over a range of ambient conditions and examples of methane plume detection.

Cavity-enhanced Thomson scattering measurements of electron density and temperature in a hollow cathode discharge.

A cavity-enhanced Thomson scattering (CETS) diagnostic has been developed to perform electron density and temperature measurements in low-density weakly ionized discharges. The diagnostic approach is based on generating a high-power beam in an optical build-up cavity and using the beam as a light source for Thomson scattering from plasma housed within the cavity. In our setup, a high-power (∼5 W) fiber laser at 1064 nm allows an intra-cavity power of 11.7 kW in a two-mirror cavity for measurements in the plume of a BaO hollow cathode discharge. A study of plasma density and temperature was performed at various operating conditions. Electron densities and temperatures in the range of ∼1012 cm-3 and ∼3 eV were measured, respectively. The high signal-to-noise ratio (SNR) of the present measurements (SNR=1100) suggests the ability to measure significantly lower density plasmas in the range of ∼3×109 to 3×1010 cm-3, thereby extending current laser Thomson scattering diagnostic capabilities.

Control of Early Flame Kernel Growth by Multi-Wavelength Laser Pulses for Enhanced Ignition.

The present contribution examines the impact of plasma dynamics and plasma-driven fluid dynamics on the flame growth of laser ignited mixtures and shows that a new dual-pulse scheme can be used to control the kernel formation process in ways that extend the lean ignition limit. We perform a comparative study between (conventional) single-pulse laser ignition (λ = 1064 nm) and a novel dual-pulse method based on combining an ultraviolet (UV) pre-ionization pulse (λ = 266 nm) with an overlapped near-infrared (NIR) energy addition pulse (λ = 1064 nm). We employ OH* chemiluminescence to visualize the evolution of the early flame kernel. For single-pulse laser ignition at lean conditions, the flame kernel separates through third lobe detachment, corresponding to high strain rates that extinguish the flame. In this work, we investigate the capabilities of the dual-pulse to control the plasma-driven fluid dynamics by adjusting the axial offset of the two focal points. In particular, we find there exists a beam waist offset whereby the resulting vorticity suppresses formation of the third lobe, consequently reducing flame stretch. With this approach, we demonstrate that the dual-pulse method enables reduced flame speeds (at early times), an extended lean limit, increased combustion efficiency, and decreased laser energy requirements.

Fabrication of Nanostructured Omniphobic and Superomniphobic Surfaces with Inexpensive CO2 Laser Engraver.

Superomniphobic surfaces (i.e., surfaces that are extremely repellent to both high surface tension liquids like water and low surface tension liquid like oils) can be fabricated through a combination of surface chemistry that imparts low solid surface energy with a re-entrant surface texture. Recently, surface texturing with lasers has received significant attention because laser texturing is scalable, solvent-free, and can produce a monolithic texture on virtually any material. In this work, we fabricated nanostructured omniphobic and superomniphobic surfaces with a variety of materials using a simple, inexpensive and commercially available CO2 laser engraver. Further, we demonstrated that the nanostructured omniphobic and superomniphobic surfaces fabricated using our laser texturing technique can be used to design patterned surfaces, surfaces with discrete domains of the desired wettability, and on-surface microfluidic devices.

Water Plume Temperature Measurements by an Unmanned Aerial System (UAS).

We report on the development and testing of a proof of principle water temperature measurement system deployed on an unmanned aerial system (UAS), for field measurements of thermal discharges into water. The primary elements of the system include a quad-copter UAS to which has been integrated, for the first time, both a thermal imaging infrared (IR) camera and an immersible probe that can be dipped below the water surface to obtain vertical water temperature profiles. The IR camera is used to take images of the overall water surface to geo-locate the plume, while the immersible probe provides quantitative temperature depth profiles at specific locations. The full system has been tested including the navigation of the UAS, its ability to safely carry the sensor payload, and the performance of both the IR camera and the temperature probe. Finally, the UAS sensor system was successfully deployed in a pilot field study at a coal burning power plant, and obtained images and temperature profiles of the thermal effluent.

Cavity-enhanced rotational Raman scattering in gases using a 20 mW near-infrared fiber laser.

A novel cavity-enhanced laser diagnostic has been developed to perform point measurements of spontaneous rotational Raman scattering. A narrow linewidth fiber laser source (1064 nm) is frequency locked to a high-finesse cavity containing the sample gas. Intracavity powers of 22 W are generated from 3.7 mW of incident laser power, corresponding to a buildup factor of 5900. A triple monochromator and a photomultiplier tube in counting mode are used to disperse and measure the scattering spectra. The system is demonstrated with rotational Raman spectra of nitrogen, oxygen, and carbon dioxide at atmospheric pressure. The approach will allow temporally and spatially resolved Raman measurements for combustion diagnostics and, by extending to higher power, Thomson scattering for diagnostics of low-density plasmas.

Open-path cavity ring-down spectroscopy for trace gas measurements in ambient air.

The present work used a near-infrared methane cavity ring-down spectroscopy (CRDS) sensor to examine performance and limitations of open-path CRDS for atmospheric measurements. A simple purge-enclosure was developed to maintain high mirror reflectivity and allowed >100 hours of operation with mirror reflectivity above 0.99996. We characterized effects of aerosols on ring-down decay signals and found the dominant effect to be fluctuations by large super-micron particles. Simple software filtering approaches were developed to combat these fluctuations allowing noise-equivalent sensitivity of ~6x10-10 cm-1HJ Hz-1/2 within a factor of ~3 of closed-path systems (based on stability of the absorption baseline). Sensor measurements were validated against known methane concentrations in a closed-path configuration, while open-path validation was performed by side-by-side comparison with a commercial closed-path system.

A high-finesse broadband optical cavity using calcium fluoride prism retroreflectors.

A high-finesse broadband optical cavity has been developed for use in the ultraviolet and visible region using Brewster-angle calcium fluoride (CaF2) prism retroreflectors. Prior to prism construction, optical loss measurements of CaF2 windows were performed using cavity ring-down spectroscopy at 250 nm. Total optical loss showed high spatial correlation with crystal birefringence, which was partially mitigated by orienting the <111> crystal axis with the laser beam. Prism reflectivity was measured using cavity ring-down spectroscopy and found to be 99.77% at 250 nm and 99.96% at 500 nm, allowing for relatively high-finesse operation over hundreds of nm bandwidth with a single cavity.

High Power Spark Delivery System Using Hollow Core Kagome Lattice Fibers.

This study examines the use of the recently developed hollow core kagome lattice fibers for delivery of high power laser pulses. Compared to other photonic crystal fibers (PCFs), the hollow core kagome fibers have larger core diameter (~50 µm), which allows for higher energy coupling in the fiber while also maintaining high beam quality at the output (M² = 1.25). We have conducted a study of the maximum deliverable energy versus laser pulse duration using a Nd:YAG laser at 1064 nm. Pulse energies as high as 30 mJ were transmitted for 30 ns pulse durations. This represents, to our knowledge; the highest laser pulse energy delivered using PCFs. Two fiber damage mechanisms were identified as damage at the fiber input and damage within the bulk of the fiber. Finally, we have demonstrated fiber delivered laser ignition on a single-cylinder gasoline direct injection engine.

High power fiber delivery for laser ignition applications.

The present contribution provides a concise review of high power fiber delivery research for laser ignition applications. The fiber delivery requirements are discussed in terms of exit energy, intensity, and beam quality. Past research using hollow core fibers, solid step-index fibers, and photonic crystal and bandgap fibers is summarized. Recent demonstrations of spark delivery using large clad step-index fibers and Kagome photonic bandgap fibers are highlighted.

Fiber-coupled ultraviolet planar laser-induced fluorescence for combustion diagnostics.

Multimode silica step-index optical fibers are examined for use in planar laser-induced fluorescence (PLIF) for combustion diagnostics using ultraviolet (UV) laser sources. The multimode step-index fibers are characterized at UV wavelengths by examining their energy damage thresholds and solarization performance. The beam quality achievable with large clad step-index multimode fibers is also studied. Emphasis is placed on simultaneously achieving high output energy and beam quality (low output M(2)). The use of multimode fibers to deliver UV pulses at 283 nm for PLIF measurements of OH radicals in a Hencken burner is demonstrated. The fiber delivery capability of UV light will benefit combustion diagnostics in hostile environments, such as augmentor and combustor rigs.

Mode coupling and output beam quality of 100-400 µm core silica fibers.

Propagation and mode coupling within relatively short (∼1-10 m) large core, nominally multimode, fibers are of interest in a number of applications. In this research, we have studied the output beam quality and mode coupling in various fibers with core diameters of 100-400 µm and lengths of 2 m. Output beam quality (M2) and mode-coupling coefficients (D) have been studied for different clad dimensions, numerical apertures, and wavelengths. The mode-coupling coefficients have been determined based on modal power diffusion considerations. The results show that D scales approximately as the inverse square of the clad dimension and inverse square root of the wavelength. Output from a 2 m length fiber of 100 µm core and 660 µm clad fiber is close to single mode (M2=1.6), while output from a 200 µm core and 745 µm clad fiber also has high beam quality.

Laser-induced breakdown spectroscopy for in-cylinder equivalence ratio measurements in laser-ignited natural gas engines.

In this contribution we present the first demonstration of simultaneous use of laser sparks for engine ignition and laser-induced breakdown spectroscopy (LIBS) measurements of in-cylinder equivalence ratios. A 1064 nm neodynium yttrium aluminum garnet (Nd:YAG) laser beam is used with an optical spark plug to ignite a single cylinder natural gas engine. The optical emission from the combustion initiating laser spark is collected through the optical spark plug and cycle-by-cycle spectra are analyzed for H(alpha)(656 nm), O(777 nm), and N(742 nm, 744 nm, and 746 nm) neutral atomic lines. The line area ratios of H(alpha)/O(777), H(alpha)/N(746), and H(alpha)/N(tot) (where N(tot) is the sum of areas of the aforementioned N lines) are correlated with equivalence ratios measured by a wide band universal exhaust gas oxygen (UEGO) sensor. Experiments are performed for input laser energy levels of 21 mJ and 26 mJ, compression ratios of 9 and 11, and equivalence ratios between 0.6 and 0.95. The results show a linear correlation (R(2) > 0.99) of line intensity ratio with equivalence ratio, thereby suggesting an engine diagnostic method for cylinder resolved equivalence ratio measurements.