Search

Summary: Background: Peripheral artery disease (PAD) impacts 3–12% of patients worldwide and is characterized by endothelial dysfunction and inflammatory pathways which are also common to venous thromboembolism (VTE), but there is a paucity of evidence regarding VTE risk in PAD patients. We investigated whether PAD is an independent risk factor for VTE. Patients and methods: We reviewed medical records of patients undergoing ABI studies at Mayo Clinic from 01/1996-02/2020. We classified patients by ABI (low [1.4]), as well as by specific low ABI subgroup: severely reduced (ABI: 0.00–0.39), moderately reduced (0.40–0.69), mildly reduced (0.70–0.90), and borderline reduced (0.91–0.99). The primary outcome was incident VTE event (acute lower extremity deep vein thrombosis or pulmonary embolism) after ABI measurement. Multivariable Cox proportional regression was used to calculate hazard ratios (HR) with 95% confidence intervals (CI) after adjusting for age, sex, active smoking, cancer, previous VTE, thrombophilia, anticoagulation, and revascularization. Results: 39,834 unique patients (mean age 66.3±14.3 years, median follow-up 34 months) were identified. 2,305 VTE events occurred in patients without PAD (13.0%), 2,218 in low ABI patients (13.0%), and 751 in elevated ABI patients (14.8%). After risk factor adjustment, VTE risk was modestly increased for PAD overall (HR: 1.12, 95% CI [1.06, 1.18]), including low ABI (HR: 1.11, 95% CI [1.04, 1.18]) and elevated ABI groups (HR: 1.15, 95% CI [1.04, 1.26]), compared to patients without PAD. The greatest VTE risk was in severely low ABI patients (HR: 1.46, 95% CI [1.31, 1.64]). Conclusions: In a large longitudinal cohort, we present strong clinical evidence of PAD, with low and elevated ABI, as an independent VTE risk factor, with the highest risk seen in patients with severely low ABI. Continued research is required to further investigate this relationship and its intersection with functional performance status to optimize VTE risk reduction or anticoagulation strategies in the PAD population.

Peripheral artery disease (PAD) prevalence increases with age, but the relation between age at PAD diagnosis and outcomes is unclear. We investigated the cardiovascular and limb outcomes of patients diagnosed with PAD at different ages. We studied patients with PAD aged ≥18 years who were diagnosed between 1996 and 2020 at Mayo Clinic. Patients were grouped by diagnosis age (50, 50 to 59, 60 to 69, ≥70 years) and ankle brachial index (ABI): low ABI (1.0) or elevated ABI (1.4). Primary outcomes were cardiovascular events (CVEs; myocardial infarction or ischemic stroke) and limb events (LEs; critical limb ischemia or amputation). Competing risk analysis was performed to calculate adjusted hazard ratios. The cohort included 22,073 patients with PAD (low ABI: 77.1%; elevated ABI: 22.9%). CVEs were observed in 8.2% of patients and LEs in 15.6%. The highest CVE risk was observed in patients diagnosed with PAD before age 50 (compared with patients diagnosed after age 70; hazard ratio 2.33 [95% confidence interval 1.95 to 2.78]). CVE risk decreased with older age at diagnosis. Although younger groups demonstrated higher LE risk, there was no clear association with diagnosis age. These patterns of risk were seen both in low and elevated ABI subgroups but in greater magnitude with elevated ABI. Younger patients diagnosed with PAD face increased risk of myocardial infarction and ischemic stroke compared with patients diagnosed at an older age. CVE risk notably exceeds LE risk. In conclusion, younger age at PAD diagnosis may be an important risk factor, which warrants more aggressive interventions focused on CVE prevention.

Atmospheric carbon dioxide (CO2) accounts for the largest radiative forcing among anthropogenic greenhouse gases. There is, therefore, a pressing need to understand the rate at which CO2 accumulates in the atmosphere, including the interannual variations (IAVs) in this rate. IAV in the CO2 growth rate is a small signal relative to the long-term trend and the mean annual cycle of atmospheric CO2, and IAV is tied to climatic variations that may provide insights into long-term carbon–climate feedbacks. Observations from the Orbiting Carbon Observatory-2 (OCO-2) mission offer a new opportunity to refine our understanding of atmospheric CO2 IAV since the satellite can measure over remote terrestrial regions and the open ocean, where traditional in situ CO2 monitoring is difficult, providing better spatial coverage compared to ground-based monitoring techniques. In this study, we analyze the IAV of column-averaged dry-air CO2 mole fraction (XCO2) from OCO-2 between September 2014 and June 2021. The amplitude of the IAV, which is calculated as the standard deviation of the time series, is up to 1.2 ppm over the continents and around 0.4 ppm over the open ocean. Across all latitudes, the OCO-2-detected XCO2 IAV shows a clear relationship with El Niño–Southern Oscillation (ENSO)-driven variations that originate in the tropics and are transported poleward. Similar, but smoother, zonal patterns of OCO-2 XCO2 IAV time series compared to ground-based in situ observations and with column observations from the Total Carbon Column Observing Network (TCCON) and the Greenhouse Gases Observing Satellite (GOSAT) show that OCO-2 observations can be used reliably to estimate IAV. Furthermore, the extensive spatial coverage of the OCO-2 satellite data leads to smoother IAV time series than those from other datasets, suggesting that OCO-2 provides new capabilities for revealing small IAV signals despite sources of noise and error that are inherent to remote-sensing datasets.

EM27/SUN devices are portable solar-viewing Fourier transform spectrometers (FTSs) that are being widely used to constrain measurements of greenhouse gas emissions and validate satellite trace gas measurements. On a 6-week-long campaign in the summer of 2018, four EM27/SUN devices were taken to five Total Carbon Column Observing Network (TCCON) stations in North America, to measure side by side, to better understand their durability, the accuracy and precision of retrievals from their trace gas measurements, and to constrain site-to-site bias among TCCON sites. We developed new EM27/SUN data products using both previous and current versions of the retrieval algorithm (GGG2014 and GGG2020) and used coincident AirCore measurements to tie the gas retrievals to the World Meteorological Organization (WMO) trace gas standard scales. We also derived air-mass-dependent correction factors for the EM27/SUN devices. Pairs of column-averaged dry-air mole fractions (denoted with an X) measured by the EM27/SUN devices remained consistent compared to each other during the entire campaign, with a 10 min averaged precision of 0.3 ppm (parts per million) for XCO2, 1.7 ppb (parts per billion) for XCH4, and 2.5 ppb for XCO. The maximum biases between TCCON stations were reduced in GGG2020 relative to GGG2014 from 1.3 to 0.5 ppm for XCO2 and from 5.4 to 4.3 ppb for XCH4 but increased for XCO from 2.2 to 6.1 ppb. The increased XCO biases in GGG2020 are driven by measurements at sites influenced by urban emissions (Caltech and the Armstrong Flight Research Center) where the priors overestimate surface CO. In addition, in 2020, one EM27/SUN instrument was sent to the Canadian Arctic TCCON station at Eureka, and side-by-side measurements were performed in March–July. In contrast to the other TCCON stations that showed an improvement in the biases with the newer version of GGG, the biases between Eureka's TCCON measurements and those from the EM27/SUN degraded with GGG2020, but this degradation was found to be caused by a temperature dependence in the EM27/SUN oxygen retrievals that is not apparent in the GGG2014 retrievals.

In order to infer greenhouse gas emissions from a source region, several top-down approaches can confirm or constrain the existing emission inventories.Due to the long-term stability of methane, the air holds a non-zero background concentration before it enters the domain of interest. This background concentration typically cannot be neglected and poses a major challenge in emission estimates from observations. Inspired by a Bayesian inversion framework [1] which inverts the background concentrations together with the emissions, we will present a novel (non-Bayesian) inversion framework that estimates the background from the observations and derives the emissions from these calculated enhancements.Background concentrations are estimated using a combination of measurements at multiple upwind sites, similar to mass balance approaches, but in a more sophisticated manner: The observed total column concentrations at the downwind site are considered to be associated with the concentrations at an upwind site if the backward trajectories calculated by STILT pass close to the respective upwind site. In a second step, the derived enhancements are attributed to the surface fluxes using the STILT calculated footprint.Methane emission estimates are derived from the total column concentrations measured with six EM27/SUN FTIR spectrometers using ground based direct sunlight spectroscopy. The measurement campaign was carried out in the San Francisco Bay Area in 2016. [1] Jones, T. S., Franklin, J. E., Chen, J., Dietrich, F., Hajny, K. D., Paetzold, J. C., Wenzel, A., Gately, C., Gottlieb, E., Parker, H., Dubey, M., Hase, F., Shepson, P. B., Mielke, L. H., and Wofsy, S. C.: Assessing Urban Methane Emissions using Column Observing Portable FTIR Spectrometers and a Novel Bayesian Inversion Framework, Atmos. Chem. Phys. https://doi.org/10.5194/acp-21-13131-2021, 2021.

Bromine activation (the production of Br in an elevated oxidation state) represents a mechanism for ozone destruction and mercury removal in the global troposphere, and has been a common feature of both polar boundary layers, often accompanied by nearly complete ozone destruction. The chemistry and budget of active bromine compounds (e.g. Br2, BrCl, HOBr) reflects the cycling of Br and ultimately its impact on the environment. Cyanogen bromide (BrCN) has recently been measured by iodide ion high resolution time-of-flight mass spectrometry (I- CIMS) during the NASA Atmospheric Tomography mission, and could be a previously unquantified participant in active Br chemistry. BrCN mixing ratios ranged from below detection limit (1.5pptv) up to as high as 48 pptv (10sec avg) and enhancements were almost exclusively confined to the polar boundary layers (PBL). Likely BrCN formation pathways involve the reactions of active Br (Br2, HOBr) with reduced nitrogen compounds. Gas phase loss processes due to reaction with radical species are likely quite slow and photolysis is known to be relatively slow. These features, and the lack of BrCN enhancements above the PBL, imply that surface reactions must be the major loss processes. Known liquid phase reactions of BrCN result in the conversion of the Br to bromide (Br-) or formation of C-Br bonded organic species, hence a loss of atmospheric active Br from that chemical cycle. Thus, accounting for the chemistry of BrCN will be an important aspect of understanding polar Br cycling.

The Orbiting Carbon Observatory 3 (OCO-3) was installed on the International Space Station (ISS) in May 2019 and will continue the observation of global CO2 and solar-induced chlorophyll fluorescence (SIF) observations using the flight spare instrument from OCO-2. This talk will focus on the science data products, early operations, abd a few highlights from early mission data.The low-inclination ISS orbit lets OCO-3 sample the tropics and sub-tropics across the full range of daylight hours with dense observations at northern and southern mid-latitudes (+/- 52º). The combination of these dense CO2 and SIF measurements provides continuity of data for global flux estimates as well as a unique opportunity to address key deficiencies in our understanding of the global carbon cycle. The instrument utilizes an agile, 2-axis pointing mechanism (PMA), providing the capability to look towards the bright reflection from the ocean and validation targets. The PMA also allows for the collection of dense datasets over 80km by 80km areas called snapshot area maps (SAMs).The in-orbit check out of the instrument was conducted through July 2019. In this phase the engineering team verified the performance of all systems, the calibration team began collecting the needed calibration data, and the mission operations team verified the performance of all measurement modes and the mission operations planning tools. Since August 2019, OCO-3 has been collecting routine nadir, glint, target, and SAM data.Target mode observations over surface-based Total Carbon Column Observing Network (TCCON) sites help to identify and minimize potential instrument biases in the OCO-3 data. Other validation activities include direct comparisons to XCO2 estimates from OCO-2 and comparisons to predictions from near-real-time models. These comparisons will be discussed and early results will be presented. In addition, several hundred SAMs have been collected over (mega-)cities, powerplants, volcanos, and other terrestrial carbon focus areas. The steadily growing number of SAM observations provides a unique dataset for scientific studies on local scales. We discuss the potential of these observations, alone and in conjunction with simultaneous observations from other space-based sensors, to yield greater insights into carbon cycle science.

Secondary organic aerosol (SOA) formation from the reaction of isoprene with nitrate radicals (NO3) is investigated in the Caltech indoor chambers. Experiments are performed in the dark and under dry conditions (RH&lt10%) using N2O5 as a source of NO3 radicals. For an initial isoprene concentration of 18.4 to 101.6 ppb, the SOA yield (defined as the ratio of the mass of organic aerosol formed to the mass of parent hydrocarbon reacted) ranges from 4.3% to 23.8%. By examining the time evolutions of gas-phase intermediate products and aerosol volume in real time, we are able to constrain the chemistry that leads to the formation of low-volatility products. Although the formation of ROOR from the reaction of two peroxy radicals (RO2) has generally been considered as a minor channel, based on the gas-phase and aerosol-phase data it appears that RO2+RO2 reaction (self reaction or cross-reaction) in the gas phase yielding ROOR products is a dominant SOA formation pathway. A wide array of organic nitrates and peroxides are identified in the aerosol formed and mechanisms for SOA formation are proposed. Using a uniform SOA yield of 10% (corresponding to Mo≅10 μg m−3), it is estimated that ~2 to 3 Tg yr−1 of SOA results from isoprene+NO3. The extent to which the results from this study can be applied to conditions in the atmosphere depends on the fate of peroxy radicals in the nighttime troposphere.

Knowledge of molecular photolysis cross sections is important for determining atmospheric lifetimes and fates of many species. A method and laser apparatus for measurement of these cross sections in the near-ultraviolet (UV) region is described. The technique is based on action spectroscopy, where the yield of a photodissociation product (in this case OH) is measured as a function of excitation energy. For compounds yielding OH, this method can be used to measure near-UV photodissociation cross section as low as 10^−23 cm^2 molecule−1. The method is applied to determine the photodissociation cross sections for methyl hydroperoxide (CH3OOH; MHP) and hydroxymethyl hydroperoxide (HOCH2OOH; HMHP) in the 305–365 nm wavelength range. The measured cross sections are in good agreement with previous measurements of absorption cross sections.