George R. Farquar

Fractal morphology, imaging and mass spectrometry of single aerosol particles in flight

The morphology of micrometre-size particulate matter is of critical importance in fields ranging from toxicology to climate science, yet these properties are surprisingly difficult to measure in the particles’ native environment. Electron microscopy requires collection of particles on a substrate; visible light scattering provides insufficient resolution; and X-ray synchrotron studies have been limited to ensembles of particles. Here we demonstrate an in situ method for imaging individual sub-micrometre particles to nanometre resolution in their native environment, using intense, coherent X-ray pulses from the Linac Coherent Light Source free-electron laser. We introduced individual aerosol particles into the pulsed X-ray beam, which is sufficiently intense that diffraction from individual particles can be measured for morphological analysis. At the same time, ion fragments ejected from the beam were analysed using mass spectrometry, to determine the composition of single aerosol particles. Our results show the extent of internal dilation symmetry of individual soot particles subject to non-equilibrium aggregation, and the surprisingly large variability in their fractal dimensions. More broadly, our methods can be extended to resolve both static and dynamic morphology of general ensembles of disordered particles. Such general morphology has implications in topics such as solvent accessibilities in proteins, vibrational energy transfer by the hydrodynamic interaction of amino acids, and large-scale production of nanoscale structures by flame synthesis.

Design and optimization of a light-emitting diode projection micro-stereolithography three-dimensional manufacturing system

The rapid manufacture of complex three-dimensional micro-scale components has eluded researchers for decades. Several additive manufacturing options have been limited by either speed or the ability to fabricate true three-dimensional structures. Projection micro-stereolithography (PμSL) is a low cost, high throughput additive fabrication technique capable of generating three-dimensional microstructures in a bottom-up, layer by layer fashion. The PμSL system is reliable and capable of manufacturing a variety of highly complex, three-dimensional structures from micro- to meso-scales with micro-scale architecture and submicron precision. Our PμSL system utilizes a reconfigurable digital mask and a 395 nm light-emitting diode (LED) array to polymerize a liquid monomer in a layer-by-layer manufacturing process. This paper discusses the critical process parameters that influence polymerization depth and structure quality. Experimental characterization and performance of the LED-based PμSL system for fabricating highly complex three-dimensional structures for a large range of applications is presented.

Toward unsupervised single-shot diffractive imaging of heterogeneous particles using X-ray free-electron lasers

Single shot diffraction imaging experiments via X-ray free-electron lasers can generate as many as hundreds of thousands of diffraction patterns of scattering objects. Recovering the real space contrast of a scattering object from these patterns currently requires a reconstruction process with user guidance in a number of steps, introducing severe bottlenecks in data processing. We present a series of measures that replace user guidance with algorithms that reconstruct contrasts in an unsupervised fashion. We demonstrate the feasibility of automating the reconstruction process by generating hundreds of contrasts obtained from soot particle diffraction experiments.

Autonomous, broad-spectrum detection of hazardous aerosols in seconds.

Actual or surrogate chemical, biological, radiological, nuclear, and explosive materials and illicit drug precursors can be rapidly detected and identified when in aerosol form by a Single-Particle Aerosol Mass Spectrometry (SPAMS) system. This entails not only the sampling of such particles but also the physical analysis and subsequent data analysis leading to a highly reliable alarm state. SPAMS hardware is briefly reviewed. SPAMS software algorithms are discussed in greater detail. A laboratory experiment involving actual threat and surrogate releases mixed with ambient background aerosols demonstrates broad-spectrum detection within seconds. Data from a field test at the San Francisco International Airport demonstrate extended field operation with an ultralow false alarm rate. Together these data sets demonstrate a significant and important advance in rapid aerosol threat detection.

Sensing the wavefront of x-ray free-electron lasers using aerosol spheres

Characterizing intense, focused x-ray free electron laser (FEL) pulses is crucial for their use in diffractive imaging. We describe how the distribution of average phase tilts and intensities on hard x-ray pulses with peak intensities of 10(21) W/m(2) can be retrieved from an ensemble of diffraction patterns produced by 70 nm-radius polystyrene spheres, in a manner that mimics wavefront sensors. Besides showing that an adaptive geometric correction may be necessary for diffraction data from randomly injected sample sources, our paper demonstrates the possibility of collecting statistics on structured pulses using only the diffraction patterns they generate and highlights the imperative to study its impact on single-particle diffractive imaging.

Single particle imaging with soft X-rays at the linac coherent light source

Results of coherent diffractive imaging experiments performed with soft X-rays (1-2 keV) at the Linac Coherent Light Source are presented. Both organic and inorganic nano-sized objects were injected into the XFEL beam as an aerosol focused with an aerodynamic lens. The high intensity and femtosecond duration of X-ray pulses produced by the Linac Coherent Light Source allow structural information to be recorded by X-ray diffraction before the particle is destroyed. Images were formed by using iterative methods to phase single shot diffraction patterns. Strategies for improving the reconstruction methods have been developed. This technique opens up exciting opportunities for biological imaging, allowing structure determination without freezing, staining or crystallization.

Detecting trace pesticides in real time using single particle aerosol mass spectrometry.

Pesticides are toxic substances and may cause unintentional harm if improperly used. The ubiquitous nature of pesticides, with frequent use in agriculture and the household, and the potential for harm that pesticides pose to non-target organisms such as wildlife, humans, and pets, demonstrate the need for rapid and effective detection and identification of these compounds. In this study, single particle aerosol mass spectrometry (SPAMS) was used to rapidly detect compounds from four classes of pesticides commonly used in agricultural and household applications. These include permethrin (pyrethroid class), malathion and dichlorvos (organophosphate class), imidacloprid (chloronicotinyl class), and carbaryl (carbamate class). Analytical standards of each compound were diluted and aerosolized using a nebulizer to create particles for analysis in the SPAMS instrument. The resultant dual-polarity time-of-flight mass spectra were then analyzed to identify the characteristic peaks of the compound in each sample. In addition, samples of commercial products containing pesticides, a commercial insecticide spray, containing permethrin, and a canine flea collar, containing carbaryl, were analyzed in their original form using SPAMS without any significant sample preparation. The characteristic mass spectral peaks of the active pesticides in these samples were identified using the mass spectra obtained earlier from the pesticide analytical standards. By successfully identifying pesticides in analytical standards and in commercial products, it is demonstrated herein that the SPAMS system may be capable of pesticide detection in numerous environmental and agricultural situations.

Aerosol and Microparticle Generation Using a Commercial Inkjet Printer

Simple modifications to widely available commercial-off-the-shelf (COTS) inkjet printers and cartridges enabled production of aerosols that were tunable in number, size, and size-distribution width. Aerosols generated from various solutions using an inkjet printer with varying control software settings were dehydrated into solid microparticles for characterization using an aerodynamic particle sizer (APS) to determine particle number and size. The duration of microdroplet and microparticle production using this method was adjustable by varying the size of the print job image sent from the control computer. The microparticles created using the inkjet printer were predominantly 1–5 μm in aerodynamic diameter. Tuning of the size of the created microparticle size-distribution was achieved by changing the solute concentration in the printed solution. The size of the dried particles increased monotonically with solute concentration as expected. The aerosol size-distribution width was customizable by varying the COTS inkjet printer control software settings. The highest quality programmed print modes produced a narrower size-distribution compared to the rapid, low quality print options available in the software. The morphology of the dehydrated microparticles was determined to be spherical using scanning electron microscopy (SEM). These experiments demonstrated the successful use of commonly accessible commercial inkjet printers and software to produce tunable and well-characterized aerosol size-distributions in an easily controlled manner. The customizable aerosols and microparticles produced using this method displayed diverse properties that may be tailored to a wide range of experimental applications. Copyright 2013 American Association for Aerosol Research

Use of Single Particle Aerosol Mass Spectrometry for the Automated Nondestructive Identification of Drugs in Multicomponent Samples

In this work, single particle aerosol mass spectrometry (SPAMS) was used to identify the active drug ingredients in samples of multicomponent over-the-counter (OTC) drug tablets with minimal damage to the tablets. OTC drug tablets in various formulations were analyzed including single active ingredient tablets and multi-ingredient tablets. Using a sampling apparatus developed in-house, micrometer-sized particles were simultaneously dislodged from tablets and introduced to the SPAMS, where dual-polarity mass spectra were obtained from individual particles. Active ingredients were identified from the parent ions and fragment ions formed from each sample, and alarm files were developed for each active ingredient, allowing successful automated identification of each compound in a mixture. The alarm algorithm developed for SPAMS correctly identified all drug compounds in all single-ingredient and multi-ingredient tablets studied. A further study demonstrated the ability of this technique to identify the active ingredient in a single tablet analyzed in the presence of several other nonidentical tablets. In situ measurements were also made by sampling directly from a drug sample in its original bottle. A single tablet embedded in 11 identical tablets of different composition was detected in this manner. Overall, this work demonstrates the ability of the SPAMS technique to detect a target drug compound both in complex tablets, i.e., multidrug ingredient tablets, and complex sampling environments, i.e., multitablet sampling sources. The technique is practically nondestructive, leaving the characteristic shape, color, and imprint of a tablet intact for further analysis. Applications of this technique may include forensic and pharmaceutical analysis.

Modular Sampling and Analysis Techniques for the Real-Time Analysis of Human Breath

At LLNL and UC Davis, we are developing several techniques for the real-time sampling and analysis of trace gases, aerosols and exhaled breath that could be useful for a modular, integrated system for breath analysis. Those techniques include single-particle bioaerosol mass spectrometry (BAMS) for the analysis of exhaled aerosol particles or droplets as well as breath samplers integrated with gas chromatography mass spectrometry (GC-MS) or MEMS-based differential mobility spectrometry (DMS). We describe these techniques and present recent data obtained from human breath or breath condensate, in particular, addressing the question of how environmental exposure influences the composition of breath.