Andrew D. Aubrey

Primordial synthesis of amines and amino acids in a 1958 Miller H2S-rich spark discharge experiment

Archived samples from a previously unreported 1958 Stanley Miller electric discharge experiment containing hydrogen sulfide (H2S) were recently discovered and analyzed using high-performance liquid chromatography and time-of-flight mass spectrometry. We report here the detection and quantification of primary amine-containing compounds in the original sample residues, which were produced via spark discharge using a gaseous mixture of H2S, CH4, NH3, and CO2. A total of 23 amino acids and 4 amines, including 7 organosulfur compounds, were detected in these samples. The major amino acids with chiral centers are racemic within the accuracy of the measurements, indicating that they are not contaminants introduced during sample storage. This experiment marks the first synthesis of sulfur amino acids from spark discharge experiments designed to imitate primordial environments. The relative yield of some amino acids, in particular the isomers of aminobutyric acid, are the highest ever found in a spark discharge experiment. The simulated primordial conditions used by Miller may serve as a model for early volcanic plume chemistry and provide insight to the possible roles such plumes may have played in abiotic organic synthesis. Additionally, the overall abundances of the synthesized amino acids in the presence of H2S are very similar to the abundances found in some carbonaceous meteorites, suggesting that H2S may have played an important role in prebiotic reactions in early solar system environments.

Sulfate minerals and organic compounds on Mars

Strong evidence for evaporitic sulfate minerals such as gypsum and jarosite has recently been found on Mars. Although organic molecules are often codeposited with terrestrial evaporitic minerals, there have been no systematic investigations of organic components in sulfate minerals. We report here the detection of organic material, including amino acids and their amine degradation products, in ancient terrestrial sulfate minerals. Amino acids and amines appear to be preserved for geologically long periods in sulfate mineral matrices. This suggests that sulfate minerals should be prime targets in the search for organic compounds, including those of biological origin, on Mars.

New insights from old bones: DNA preservation and degradation in permafrost preserved mammoth remains

Despite being plagued by heavily degraded DNA in palaeontological remains, most studies addressing the state of DNA degradation have been limited to types of damage which do not pose a hindrance to Taq polymerase during PCR. Application of serial qPCR to the two fractions obtained during extraction (demineralization and protein digest) from six permafrost mammoth bones and one partially degraded modern elephant bone has enabled further insight into the changes which endogenous DNA is subjected to during diagenesis. We show here that both fractions exhibit individual qualities in terms of the prevailing type of DNA (i.e. mitochondrial versus nuclear DNA) as well as the extent of damage, and in addition observed a highly variable ratio of mitochondrial to nuclear DNA among the six mammoth samples. While there is evidence suggesting that mitochondrial DNA is better preserved than nuclear DNA in ancient permafrost samples, we find the initial DNA concentration in the bone tissue to be as relevant for the total accessible mitochondrial DNA as the extent of DNA degradation post-mortem. We also evaluate the general applicability of indirect measures of preservation such as amino-acid racemization, bone crystallinity index and thermal age to these exceptionally well-preserved samples.

New method for estimating bacterial cell abundances in natural samples by use of sublimation

ABSTRACT We have developed a new method based on the sublimation of adenine from Escherichia coli to estimate bacterial cell counts in natural samples. To demonstrate this technique, several types of natural samples, including beach sand, seawater, deep-sea sediment, and two soil samples from the Atacama Desert, were heated to a temperature of 500°C for several seconds under reduced pressure. The sublimate was collected on a cold finger, and the amount of adenine released from the samples was then determined by high-performance liquid chromatography with UV absorbance detection. Based on the total amount of adenine recovered from DNA and RNA in these samples, we estimated bacterial cell counts ranging from ∼105 to 109E. coli cell equivalents per gram. For most of these samples, the sublimation-based cell counts were in agreement with total bacterial counts obtained by traditional DAPI (4,6-diamidino-2-phenylindole) staining.

Airborne methane remote measurements reveal heavy-tail flux distribution in Four Corners region

Significance Fugitive methane emissions are thought to often exhibit a heavy-tail distribution (more high-emission sources than expected in a normal distribution), and thus efficient mitigation is possible if we locate the strongest emitters. Here we demonstrate airborne remote measurements of methane plumes at 1- to 3-m ground resolution over the Four Corners region. We identified more than 250 point sources, whose emissions followed a lognormal distribution, a heavy-tail characteristic. The top 10% of emitters explain about half of the total observed point source contribution and ∼1/4 the total basin emissions. This work demonstrates the capability of real-time airborne imaging spectroscopy to perform detection and categorization of methane point sources in extended geographical areas with immediate input for emissions abatement. Methane (CH4) impacts climate as the second strongest anthropogenic greenhouse gas and air quality by influencing tropospheric ozone levels. Space-based observations have identified the Four Corners region in the Southwest United States as an area of large CH4 enhancements. We conducted an airborne campaign in Four Corners during April 2015 with the next-generation Airborne Visible/Infrared Imaging Spectrometer (near-infrared) and Hyperspectral Thermal Emission Spectrometer (thermal infrared) imaging spectrometers to better understand the source of methane by measuring methane plumes at 1- to 3-m spatial resolution. Our analysis detected more than 250 individual methane plumes from fossil fuel harvesting, processing, and distributing infrastructures, spanning an emission range from the detection limit ∼ 2 kg/h to 5 kg/h through ∼ 5,000 kg/h. Observed sources include gas processing facilities, storage tanks, pipeline leaks, and well pads, as well as a coal mine venting shaft. Overall, plume enhancements and inferred fluxes follow a lognormal distribution, with the top 10% emitters contributing 49 to 66% to the inferred total point source flux of 0.23 Tg/y to 0.39 Tg/y. With the observed confirmation of a lognormal emission distribution, this airborne observing strategy and its ability to locate previously unknown point sources in real time provides an efficient and effective method to identify and mitigate major emissions contributors over a wide geographic area. With improved instrumentation, this capability scales to spaceborne applications [Thompson DR, et al. (2016) Geophys Res Lett 43(12):6571–6578]. Further illustration of this potential is demonstrated with two detected, confirmed, and repaired pipeline leaks during the campaign.

The Airborne Methane Plume Spectrometer (AMPS): Quantitative imaging of methane plumes in real time

The Airborne Methane Plume Spectrometer (AMPS) is a mature instrument concept that is ready for development at the Jet Propulsion Laboratory (JPL). At its core is a novel high-resolution imaging spectrometer that records solar reflected light between 1.99 and 2.42 pm at 1 nm resolution, including strong methane (CH4) bands in the short-wave infrared. The push-broom spectrometer will leverage recent advancements in grating design and large-format 2D focal plane arrays to enable - for the first time - the high spectral resolution necessary for trace gas retrievals combined with high-performance imaging capabilities developed for surface remote sensing. AMPS features a 36° field of view with 600 resolved spatial elements across track (1 mRad) and 431 pixels in the spectral dimension. All other aspects of the instrument, such as the telescope, cryo-cooler, image stabilizer, GPS, are identical to available airborne JPL spectrometers in operation. The AMPS design is based on the next generation Airborne Visible Infrared Imaging Spectrometer (AVIRIS-NG), which has been used for high resolution mapping of CH4 concentrations from a controlled release experiment [1] and over existing natural gas fields [2]. A real time CH4 plume detection capability originally developed for AVIRIS-NG and successfully demonstrated over oil fields [3] will also be implemented with AMPS. This will facilitate surveys over existing oil and gas fields to identify and attribute CH4 emissions to individual point source locations, permit adaptive surveys with repeat imaging of suspected sources, and allow real time communication to site operators or ground crews equipped with additional instruments to verify observed plumes. AMPS will enable quantitative imaging of CH4 plumes at unprecedented spatial resolution and precision. Using a slow moving platform such as a helicopter at 100 m flight altitude (60 m image swath) will permit imaging CH4 enhancements at 10 cm spatial resolution and an unprecedented accuracy of 0.05 g CH4/m2. This will allow robust detection of CH4 emissions as low as 0.17 m3/h (6 standard cubic feet per hour), an order of magnitude smaller than what current airborne systems can detect. Using fixed-wing aircraft, AMPS can also be flown faster and higher (1 to 8 km flight altitude), thereby providing larger image swaths (0.6 to 4.8 km swaths respectively) and effective large scale surveys. Mapping CH4 emissions to individual point source locations could allow site operators to identify and mitigate these emissions, which reflect both a potential safety hazard and lost revenue. For the regulatory and scientific communities, understanding the distribution (spatial, temporal) and size of these emissions is of interest given the large uncertainties associated with anthropogenic emissions, including industrial point source emissions and fugitive CH4 from oil and gas infrastructure.

Crosscutting airborne remote sensing technologies for oil and gas and earth science applications

Airborne imaging spectroscopy has evolved dramatically since the 1980s as a robust remote sensing technique used to generate 2-dimensional maps of surface properties over large spatial areas. Traditional applications for passive airborne imaging spectroscopy include interrogation of surface composition, such as mapping of vegetation diversity and surface geological composition. Two recent applications are particularly relevant to the needs of both the oil and gas as well as government sectors: quantification of surficial hydrocarbon thickness in aquatic environments and mapping atmospheric greenhouse gas components. These techniques provide valuable capabilities for petroleum seepage in addition to detection and quantification of fugitive emissions. New empirical data that provides insight into the source strength of anthropogenic methane will be reviewed, with particular emphasis on the evolving constraints enabled by new methane remote sensing techniques. Contemporary studies attribute high-strength point sources as significantly contributing to the national methane inventory and underscore the need for high performance remote sensing technologies that provide quantitative leak detection. Imaging sensors that map spatial distributions of methane anomalies provide effective techniques to detect, localize, and quantify fugitive leaks. Airborne remote sensing instruments provide the unique combination of high spatial resolution (<1 m) and large coverage required to directly attribute methane emissions to individual emission sources. This capability cannot currently be achieved using spaceborne sensors. In this study, results from recent NASA remote sensing field experiments focused on point-source leak detection, will be highlighted. This includes existing quantitative capabilities for oil and methane using state-of-the-art airborne remote sensing instruments. While these capabilities are of interest to NASA for assessment of environmental impact and global climate change, industry similarly seeks to detect and localize leaks of both oil and methane across operating fields. In some cases, higher sensitivities desired for upstream and downstream applications can only be provided by new airborne remote sensing instruments tailored specifically for a given application. There exists a unique opportunity for alignment of efforts between commercial and government sectors to advance the next generation of instruments to provide more sensitive leak detection capabilities, including those for quantitative source strength determination. Figure 1. Concept of airborne imaging spectroscopy (Murai, 1995).