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Dual-Comb Spectroscopy to Tethered Balloon System (DCS to TBS) Field Campaign Report
There is a critical need for the ability to detect, quantify, and attribute sources and sinks of greenhouse gases (GHGs) with high temporal and spatial resolution. Current methods are typically based on continuously operating near-surface point sensors or intermittent aerial/satellite observations. Dual optical frequency comb spectroscopy (“dual-comb spectroscopy”; DCS) is a laser-based technique that can bridge this sensing gap by providing high-precision, high-accuracy, and high-temporal-resolution detection and quantification of trace gases over kilometer-length scales, connecting local and regional observations. A single DCS system can also provide spatial resolution for source/sink attribution with the addition of a few minor optical elements, enabling cross-validation of other observations (e.g., Total Carbon Column Observing Network [TCCON], Orbiting Carbon Observatory [OCO-2/3], Greenhouse Gases Observing Satellite [GOSAT-1/2][).
TBS FROST Data from 2023 at SGP C1
The FROST provides chemical analysis of four time-resolved sorbent samples on a LECO GCxGC Bench Time of Flight Mass Spectrometer, using a Gerstel MPS Thermal Desorption System. Samples collected via FROST can be analyzed on one of two Sandia National Laboratories' instruments. One instrument will provide ultra-high mass spectrometer resolution (up to four decimal points or m/z data) and can be used for identification of true unknowns. Data can include suspected formulas of species not included in any current mass spectra database. This instrument also has a low limit of detection of known species (tens of femtogram range). The second instrument can provide an order of magnitude lower limits of detection (into the single-digit femtogram range) for known species currently in mass spectra databases. This system is also more resilient to environmental samples that contain higher levels of moisture.
Back trajectories for TBS flights (c1-level)
The ARMTRAJ VAP provides four trajectory datasets initialized at ARM deployment coordinates and configured using ARM datasets. The four trajectory datasets support aerosol, cloud, and planetary boundary layer research. Trajectory calculations use the HYSPLIT model informed by the ERA5 reanalysis dataset at its highest spatial resolution (~31 km). For each sample in each of the four datasets, HYSPLIT will also be run at multiple starting locations surrounding ARM deployments, enabling an ensemble of runs from which the mean and variability (estimated uncertainty) of each sample's trajectory coordinates, thermodynamic properties, or other fields will be reported.
Vertical column dual-comb spectroscopy to a TBS
Open-path dual-frequency-comb spectroscopy (DCS) is a broadband, high spectral resolution, and high precision method for measuring gas concentrations over kilometer-scale paths. It has been used for detection and quantification of emissions of pollutants, hazardous gasses, and greenhouse gasses (GHGs). DCS has been shown to measure trace-gas mixing ratios with 0.14%-0.4% agreement between instruments. To achieve high signal-to-noise ratios (SNRs) with DCS, comb light is targeted onto a retroreflector at the end of the measurement path, which returns the signal to a detector co-located with the launch signal. Installing the retroreflector on a mobile platform such as a balloon or unmanned aerial vehicle (UAV) extends the capabilities of DCS by enabling variable path lengths, greater mobility, and access to higher altitudes. Mobile-target DCS has many uses in plume and leak detection, emissions modeling, and planetary boundary layer (PBL) studies. It is a promising method for observing vertical distributions of GHGs and mixing processes in the PBL, which are difficult to measure but important for pollution and climate monitoring as well as for understanding transport of gasses through the atmosphere. Tethered balloons are an intriguing platform because they enable longer flight durations and higher altitudes than easily obtainable with a UAV and thus allow for column measurements up to and above the PBL. New measurements completed in October/November 2024 reach the highest altitudes above ground level yet achieved by mobile-target DCS. For these measurements, the retroreflector was mounted on a 7 m diameter tethered helium balloon. An actively tracking gimbal on the ground holds the DCS launch telescope and keeps the 5 cm beam pointed onto the retroreflector while the balloon is lifted, lowered, and moved by wind and turbulence.
Combined Effects of Spaceflight and Age in Astronauts as Assessed by Areal Bone Mineral Density [BMD] and Trabecular Bone Score
Spaceflight is a potential risk factor for secondary osteoporosis in astronauts. Although lumbar spine (LS) BMD declines rapidly, more than expected for age, there have been no fragility fractures in astronauts that can clearly be attributed to spaceflight. Recently, astronauts have been returning from 6‐month spaceflights with absolute BMD still above young adult mean BMD. In spite of these BMD measurements, we project that the rapid loss in bone mass over long‐duration spaceflight affects the bone microarchitecture of the LS which might predispose astronauts to premature vertebral fractures. Thus, we evaluated TBS, a novel texture index correlated with vertebral bone microarchitecture, as a means of monitoring changes to bone microarchitecture in astronauts as they age. We previously reported that TBS detects an effect of spaceflight (~6‐month duration), independent of BMD, in 51 astronauts (47+/‐4 y) (Smith et al, J Clin Densitometry 2014). Hence, TBS was evaluated in serial DXA scans (Hologic Discovery W) conducted triennially in all active and retired astronauts and more frequently (before spaceflight, after spaceflight and until recovery) in the subset of astronauts flying 4‐6‐ month missions. We used non‐linear models to describe trends in observations (BMD or TBS) plotted as a function of astronaut age. We fitted 1175 observations of 311 astronauts, pre‐flight and then postflight starting 3 years after landing or after astronaut's BMD for LS was restored to within 2% of preflight BMD. Observations were then grouped and defined as follows: 1) LD: after exposure to at least one long‐duration spaceflight > 100 days and 2) SD: before LD and after exposure to at least one short-duration spaceflight < 30 days. Data from males and females were analyzed separately. Models of SD observations revealed that TBS and BMD had similar curvilinear declines with age for both male and female astronauts. However, models of LD observations showed TBS declining with age while BMD appeared stable or trending upward. For females (n=8) LD observations were too few to discern a trend. Notably, models describing trends in TBS appeared to be more sensitive to the effects of age than the models for BMD. We conclude that TBS may provide an additional index for the lumbar spine to monitor the combined changes due to spaceflight and due to aging. This increased knowledge may enhance the ability to identify an intervention trigger for premature vertebral fractures in astronauts.
Lewis Acid Supported Nickel Nitrenoids
Abstract Metalation of the polynucleating ligand F,tbs LH 6 (1,3,5‐C 6 H 9 (NC 6 H 3 −4‐F−2‐NSiMe 2 t Bu) 3 ) with two equivalents of Zn(N(SiMe 3 ) 2 ) 2 affords the dinuclear product ( F,tbs LH 2 )Zn 2 ( 1 ), which can be further deprotonated to yield ( F,tbs L)Zn 2 Li 2 (OEt 2 ) 4 ( 2 ). Transmetalation of 2 with NiCl 2 (py) 2 yields the heterometallic, trinuclear cluster ( F,tbs L)Zn 2 Ni(py) ( 3 ). Reduction of 3 with KC 8 affords [KC 222 ][( F,tbs L)Zn 2 Ni] ( 4 ) which features a monovalent Ni centre. Addition of 1‐adamantyl azide to 4 generates the bridging μ 3 ‐nitrenoid adduct [K(THF) 3 ][( F,tbs L)Zn 2 Ni(μ 3 ‐NAd)] ( 5 ). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state ( S = ). Cyclic voltammetry of 5 reveals two fully reversible redox events. The dianionic nitrenoid [K 2 (THF) 9 ][( F,tbs L)Zn 2 Ni(μ 3 ‐NAd)] ( 6 ) was isolated and characterized while the neutral redox isomer was observed to undergo both intra‐ and intermolecular H‐atom abstraction processes. Ni K‐edge XAS studies suggest a divalent oxidation state for the Ni centres in both the monoanionic and dianionic [Zn 2 Ni] nitrenoid complexes. However, DFT analysis suggests Ni‐borne oxidation for 5 .
Lewis Acid Supported Nickel Nitrenoids
Metalation of the polynucleating ligand F,tbs LH 6 (1,3,5-C 6 H 9 (NC 6 H 3 −4-F−2-NSiMe 2 t Bu) 3 ) with two equivalents of Zn(N(SiMe 3 ) 2 ) 2 affords the dinuclear product ( F,tbs LH 2 )Zn 2 (1), which can be further deprotonated to yield ( F,tbs L)Zn 2 Li 2 (OEt 2 ) 4 (2). Transmetalation of 2 with NiCl 2 (py) 2 yields the heterometallic, trinuclear cluster ( F,tbs L)Zn 2 Ni(py) (3). Reduction of 3 with KC 8 affords [KC 222 ][( F,tbs L)Zn 2 Ni] (4) which features a monovalent Ni centre. Addition of 1-adamantyl azide to 4 generates the bridging μ 3 -nitrenoid adduct [K(THF) 3 ][( F,tbs L)Zn 2 Ni(μ 3 -NAd)] (5). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state (S = 1/2). Cyclic voltammetry of 5 reveals two fully reversible redox events. The dianionic nitrenoid [K 2 (THF) 9 ][( F,tbs L)Zn 2 Ni(μ 3 -NAd)] (6) was isolated and characterized while the neutral redox isomer was observed to undergo both intra- and intermolecular H-atom abstraction processes. Here, Ni K-edge XAS studies suggest a divalent oxidation state for the Ni centres in both the monoanionic and dianionic [Zn 2 Ni] nitrenoid complexes. However, DFT analysis suggests Ni-borne oxidation for 5.
Chloroplast SRP43 autonomously protects chlorophyll biosynthesis proteins against heat shock
The assembly of light-harvesting chlorophyll-binding proteins (LHCPs) is coordinated with chlorophyll biosynthesis during chloroplast development. The ATP-independent chaperone known as chloroplast signal recognition particle 43 (cpSRP43) mediates post-translational LHCP targeting to the thylakoid membrane and also participates in tetrapyrrole biosynthesis (TBS). How these distinct actions of cpSRP43 are controlled has remained unclear. Here, we demonstrate that cpSRP43 effectively protects several TBS proteins from heat-induced aggregation and enhances their stability during leaf greening and heat shock. While the substrate-binding domain of cpSRP43 is sufficient for chaperoning LHCPs, the stabilization of TBS clients requires the chromodomain 2 of the protein. Strikingly, cpSRP54—which activates cpSRP43’s LHCP-targeted function—inhibits the chaperone activity of cpSRP43 towards TBS proteins. High temperature weakens the interaction of cpSRP54 with cpSRP43, thus freeing cpSRP43 to interact with and protect the integrity of TBS proteins. Our data indicate that the temperature sensitivity of the cpSRP43–cpSRP54 complex enables cpSRP43 to serve as an autonomous chaperone for the thermoprotection of TBS proteins.
Space Station Freedom viewed as a 'tight building'
The Space Station Freedom (SSF), with a 30-year projected lifetime and a completely closed-loop Environmental Control and Life Support System (ECLSS), is perhaps the ultimate 'tight building'. Recognizing the potential for the development of 'tight building syndrome' (TBS), and initiating actions to minimize possible TBS occurrences on SSF, requires a multidisciplinary approach that begins with appropriate design concerns and ends with detection and control measures on board SSF. This paper presents a brief summary of current experience with TBS on earth. Air contamination, including volatile organic compounds and microorganisms, is the focus of the discussion. Preventive steps to avoid TBS, control of environmental factors that may lead to TBS, and use of real-time instrumentation for the detection of potential causes of TBS are also outlined.
Global Assimilation of L-Band Brightness Temperature Observations from SMAP and SMOS into the Catchment Land Surface Model and Contribution to the Skill of Soil Moisture Estimates
The Soil Moisture Active Passive (SMAP) and Soil Moisture Ocean Salinity (SMOS) missions provide global observations of L-band (1.4 GHz) passive microwave brightness temperature (Tb) observations at a resolution of ~40 km every 2-3 days. These observations have been available since 2015 from SMAP and since 2010 from SMOS.Soil moisture estimates from the separate assimilation of SMAP and SMOS Tb observations into land surface models were previously shown to improve over model-only estimates, thereby demonstrating the value of assimilating L-band Tb observations for soil moisture estimation. The assimilation experiments documented in the literature do not, however, establish whether the joint assimilation of SMAP and SMOS Tbs improves the skill of the resulting soil moisture estimates beyond what can be achieved with either set of observations alone. Moreover, because the published SMAP and SMOS results used different assimilation systems and configurations and applied different evaluation data and procedures, it is unclear whether the assimilation of SMAP-only or SMOS-only Tbs results in better soil moisture skill. In this presentation, we compare the results of three separate assimilation experiments for the period from April 2015 to present. The experiments utilize the SMAP Level-4 Soil Moisture (L4_SM) algorithm, which assimilates L-band Tb observations into the NASA Catchment land surface model using a spatially distributed ensemble Kalman filter. Specifically, the three experiments presented here assimilate (i) SMAP Tbs only, as in the L4_SM product, (ii) SMOS Tbs only, after interpolation of 40° incidence angle, and (iii) both SMAP and SMOS Tbs. In all other respects, the configuration of three experiments is identical, as is the validation of the output. Preliminary results suggest that the joint assimilation of SMAP and SMOS Tbs yields the most skillful soil moisture estimates when compared to independent in situ measurements. Moreover, the skill of the SMAP-only assimilation exceeds that of the SMOS-only assimilation. The presentation provides an in-depth evaluation of the skill of the assimilation estimates vs. independent in situ and satellite measurements and in terms of statistics of the observation-minus-forecast residuals and analysis increments.
In Situ Cloud Measurements at AMF3 Field Campaign Report
This campaign is a follow-up project to the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility field campaign entitled Cloud Droplet Measurement System for TBS that was focused on integration of the Mesa Photonics' cloud droplet measurement system (CDMS) into the DOE ARM tethered balloon system (TBS) and its initial field testing at ARM’s Southern Great Plains (SGP) atmospheric observatory in February–March 2020. The CDMS performs in situ measurement of droplet size distribution function and droplet number density in clouds. These characteristics are important cloud microphysical properties that are critical input parameters for atmospheric models and are also useful for proper calibration and validation of performance of other atmospheric measurement instrumentation. The overall goals of this campaign were to deploy the CDMS on the DOE ARM TBS, test its compatibility with the TBS under relevant conditions, and perform a series of in-cloud measurements at the third ARM Mobile Facility (AMF3) at Oliktok Point, Alaska. The TBS flights were conducted on November 12–19, 2020.
Regional Variability in Convection and Rain Retrievals from the TRMM Microwave Imager (TMI)
Precipitation Radar (PR) on board the TRMM satellite shows that the average height of 30 dBz in convective rain areas of the tropics varies significantly from one region to the other. When the convection is weak this height is shallow and when convection is strong this height extends deeper into the troposphere. The brightness temperature (Tb) measured by the microwave radiometer by itself does not reflect this nature of convection satisfactorily. Radiative transfer simulations of Tbs reveal that this could be due to the variations in the vertical distribution of optically active water and ice hydrometeors and their density, shape, and size. These variations are not coupled uniquely to the strength of the convective updrafts, and as a result the Tbs do not reflect properly the convective strength indicated by PR. Because of this deficiency in the Tbs the rain rate deduced from them differs from that of PR. For this reason, to improve the estimation of rain rate we have developed an empirical method. In this method a parameter based on the areal extent of the Tbs that exceed a certain magnitude is included along with the Tbs. Rain rate deduced with this approach is better correlated with that of PR when compared to the current Version 5 operational algorithm. The percentage of rain volume as a function of rain rate, for a given region of 5deg lat. X 5deg long. over a period of three months, deduced from this method, is also in better agreement with that of the PR.
Impact of Surface Roughness on AMSR-E Sea Ice Products
This paper examines the sensitivity of Advanced Microwave Scanning Radiometer (AMSR-E) brightness temperatures (Tbs) to surface roughness by a using radiative transfer model to simulate AMSR-E Tbs as a function of incidence angle at which the surface is viewed. The simulated Tbs are then used to examine the influence that surface roughness has on two operational sea ice algorithms, namely: 1) the National Aeronautics and Space Administration Team (NT) algorithm and 2) the enhanced NT algorithm, as well as the impact of roughness on the AMSR-E snow depth algorithm. Surface snow and ice data collected during the AMSR-Ice03 field campaign held in March 2003 near Barrow, AK, were used to force the radiative transfer model, and resultant modeled Tbs are compared with airborne passive microwave observations from the Polarimetric Scanning Radiometer. Results indicate that passive microwave Tbs are very sensitive even to small variations in incidence angle, which can cause either an over or underestimation of the true amount of sea ice in the pixel area viewed. For example, this paper showed that if the sea ice areas modeled in this paper mere assumed to be completely smooth, sea ice concentrations were underestimated by nearly 14% using the NT sea ice algorithm and by 7% using the enhanced NT algorithm. A comparison of polarization ratios (PRs) at 10.7,18.7, and 37 GHz indicates that each channel responds to different degrees of surface roughness and suggests that the PR at 10.7 GHz can be useful for identifying locations of heavily ridged or rubbled ice. Using the PR at 10.7 GHz to derive an "effective" viewing angle, which is used as a proxy for surface roughness, resulted in more accurate retrievals of sea ice concentration for both algorithms. The AMSR-E snow depth algorithm was found to be extremely sensitive to instrument calibration and sensor viewing angle, and it is concluded that more work is needed to investigate the sensitivity of the gradient ratio at 37 and 18.7 GHz to these factors to improve snow depth retrievals from spaceborne passive microwave sensors.
Quantitative insights into the dislocation source behavior of twin boundaries suggest a new dislocation source mechanism
Pop-in statistics from nanoindentation with spherical indenters are used to determine the stress required to activate dislocation sources in twin boundaries (TBs) in copper and its alloys. The TB source activation stress is smaller than that needed for bulk single crystals, irrespective of the indenter size, dislocation density and stacking fault energy. Because an array of pre-existing Frank partial dislocations is present at a TB, we propose that dislocation emission from the TB occurs by the Frank partials splitting into Shockley partials moving along the TB plane and perfect lattice dislocations, both of which are mobile. The proposed mechanism is supported by recent high resolution transmission electron microscopy images in deformed nanotwinned (NT) metals and may help to explain some of the superior properties of nanotwinned metals (e.g. high strength and good ductility), as well as the process of detwinning by the collective formation and motion of Shockley partial dislocations along TBs.
Tethered Balloon System Ozone Profiles during CoURAGE Summer Intensive Operational Period Field Campaign Report
During the summer IOP, the small ARM field campaign CRGTBSO3 collected measurements to gain an improved understanding of differences between the atmospheric composition in and just above the marine layer at the CoURAGE TBS site near the eastern shore of Chesapeake Bay. CRGTBSO3 included guest instrumentation with ozone (O 3 ) profile measurements on the TBS and surface O3 and meteorological measurements at the TBS site. An En-Sci 2Z electrochemical cell (ECC) ozonesonde (Komhyr 1969, 1986, Witte et al. 2018) was included on the TBS. The ozonesonde was connected to an InterMet iMet-4RSB radiosonde, and the overall data collected included vertical profiles of ozone, relative humidity, temperature, pressure, and altitude. The CRGTBSO3 iMet-4 radiosonde data is identical to that of the iMet in the Tethered Balloon System Merged Data Product (TBSMERGED; Gaustad and Dexheimer 2025). The TBSMERGED data product also includes meteorological data from a different sensor, the iMet XQ2. In some cases, the iMet XQ2 relative humidity (RH) data may be more accurate than the iMet-4, such as for some instances when the iMet-4 RH data stays at 100% for an extended period throughout a profile.
Optical properties and composition of viscous organic particles found in the Southern Great Plains
Abstract. Atmospheric high-viscosity organic particles (HVOPs) were observed in samples of ambient aerosols collected in April and May 2016 in the Southern Great Plains of the United States. These particles were apportioned as either airborne soil organic particles (ASOPs) or tar balls (TBs) from biomass burning based on spetro-microscopic imaging and assessments of meteorological records of smoke and precipitation data. Regardless of their apportionment, the number fractions of HVOPs were positively correlated (R2=0.85) with increased values of absorption Ångström exponent (AAE) measured in situ for ambient aerosol at the site. Extending this correlation to 100 % HVOPs yields an AAE of 2.6, similar to previous literature reports of the class of light-absorbing organic particles known as brown carbon (BrC). One out of the three samples investigated had a significant number of ASOPs, while the other two samples contained TBs. Although there are chemical similarities between ASOPs and TBs, they can be distinguished based on composition inferred from near-edge absorption X-ray fine structure (NEXAFS) spectroscopy. ASOPs were distinguished from TBs based on their average -COOH/C=C and -COOH/COH peak ratios, with ASOPs having lower ratios. NEXAFS spectra of filtered soil organic brine particles nebulized from field samples of standing water deposited after rain were consistent with ASOPs when laboratory particles were generated by bubble bursting at the air–organic brine interface. However, particles generated by nebulizing the bulk volume of soil organic brine had a particle composition different from ASOPs. These observations are consistent with the raindrop generation mechanism responsible for ASOP emissions in the area of study. In contrast, nebulized samples carry with them higher fractions of soil inorganics dissolved in the bulk volume of soil brine, which are not aerosolized by the raindrop mechanism. Our results support the bubble bursting mechanism of particle generation during rainfall resulting in the ejection of soil organics into the atmosphere. In addition, our results show that ASOPs may only be atmospherically relevant during times when suitable emission conditions are met.