ASU Scholarship Showcase

S-cysteinylated albumin and methionine-oxidized apolipoprotein A-I (apoA-I) have been posed as candidate markers of diseases associated with oxidative stress. Here, a dilute-and-shoot form of LC–electrospray ionization–MS requiring half a microliter of blood plasma was employed to simultaneously quantify the relative abundance of these oxidized proteoforms in samples stored at −80 °C, −20 °C, and room temperature and exposed to multiple freeze-thaw cycles and other adverse conditions in order to assess the possibility that protein oxidation may occur as a result of poor sample storage or handling. Samples from a healthy donor and a participant with poorly controlled type 2 diabetes started at the same low level of protein oxidation and behaved similarly; significant increases in albumin oxidation via S-cysteinylation were found to occur within hours at room temperature and days at −20 °C. Methionine oxidation of apoA-I took place on a longer time scale, setting in after albumin oxidation reached a plateau. Freeze–thaw cycles had a minimal effect on protein oxidation. In matched collections, protein oxidation in serum was the same as that in plasma. Albumin and apoA-I oxidation were not affected by sample headspace or the degree to which vials were sealed. ApoA-I, however, was unexpectedly found to oxidize faster in samples with lower surface-area-to-volume ratios. An initial survey of samples from patients with inflammatory conditions normally associated with elevated oxidative stress-including acute myocardial infarction and prostate cancer—demonstrated a lack of detectable apoA-I oxidation. Albumin S-cysteinylation in these samples was consistent with known but relatively brief exposures to temperatures above −30 °C (the freezing point of blood plasma). Given their properties and ease of analysis, these oxidized proteoforms, once fully validated, may represent the first markers of blood plasma specimen integrity based on direct measurement of oxidative molecular damage that can occur under suboptimal storage conditions.

A globally integrated carbon observation and analysis system is needed to improve the fundamental understanding of the global carbon cycle, to improve our ability to project future changes, and to verify the effectiveness of policies aiming to reduce greenhouse gas emissions and increase carbon sequestration. Building an integrated carbon observation system requires transformational advances from the existing sparse, exploratory framework towards a dense, robust, and sustained system in all components: anthropogenic emissions, the atmosphere, the ocean, and the terrestrial biosphere. The paper is addressed to scientists, policymakers, and funding agencies who need to have a global picture of the current state of the (diverse) carbon observations.

We identify the current state of carbon observations, and the needs and notional requirements for a global integrated carbon observation system that can be built in the next decade. A key conclusion is the substantial expansion of the ground-based observation networks required to reach the high spatial resolution for CO₂ and CH₄ fluxes, and for carbon stocks for addressing policy-relevant objectives, and attributing flux changes to underlying processes in each region. In order to establish flux and stock diagnostics over areas such as the southern oceans, tropical forests, and the Arctic, in situ observations will have to be complemented with remote-sensing measurements. Remote sensing offers the advantage of dense spatial coverage and frequent revisit. A key challenge is to bring remote-sensing measurements to a level of long-term consistency and accuracy so that they can be efficiently combined in models to reduce uncertainties, in synergy with ground-based data.

Bringing tight observational constraints on fossil fuel and land use change emissions will be the biggest challenge for deployment of a policy-relevant integrated carbon observation system. This will require in situ and remotely sensed data at much higher resolution and density than currently achieved for natural fluxes, although over a small land area (cities, industrial sites, power plants), as well as the inclusion of fossil fuel CO₂ proxy measurements such as radiocarbon in CO₂ and carbon-fuel combustion tracers. Additionally, a policy-relevant carbon monitoring system should also provide mechanisms for reconciling regional top-down (atmosphere-based) and bottom-up (surface-based) flux estimates across the range of spatial and temporal scales relevant to mitigation policies. In addition, uncertainties for each observation data-stream should be assessed. The success of the system will rely on long-term commitments to monitoring, on improved international collaboration to fill gaps in the current observations, on sustained efforts to improve access to the different data streams and make databases interoperable, and on the calibration of each component of the system to agreed-upon international scales.

Deposits of dark material appear on Vesta’s surface as features of relatively low-albedo in the visible wavelength range of Dawn’s camera and spectrometer. Mixed with the regolith and partially excavated by younger impacts, the material is exposed as individual layered outcrops in crater walls or ejecta patches, having been uncovered and broken up by the impact. Dark fans on crater walls and dark deposits on crater floors are the result of gravity-driven mass wasting triggered by steep slopes and impact seismicity. The fact that dark material is mixed with impact ejecta indicates that it has been processed together with the ejected material. Some small craters display continuous dark ejecta similar to lunar dark-halo impact craters, indicating that the impact excavated the material from beneath a higher-albedo surface. The asymmetric distribution of dark material in impact craters and ejecta suggests non-continuous distribution in the local subsurface. Some positive-relief dark edifices appear to be impact-sculpted hills with dark material distributed over the hill slopes.

Dark features inside and outside of craters are in some places arranged as linear outcrops along scarps or as dark streaks perpendicular to the local topography. The spectral characteristics of the dark material resemble that of Vesta’s regolith. Dark material is distributed unevenly across Vesta’s surface with clusters of all types of dark material exposures. On a local scale, some craters expose or are associated with dark material, while others in the immediate vicinity do not show evidence for dark material. While the variety of surface exposures of dark material and their different geological correlations with surface features, as well as their uneven distribution, indicate a globally inhomogeneous distribution in the subsurface, the dark material seems to be correlated with the rim and ejecta of the older Veneneia south polar basin structure. The origin of the dark material is still being debated, however, the geological analysis suggests that it is exogenic, from carbon-rich low-velocity impactors, rather than endogenic, from freshly exposed mafic material or melt, exposed or created by impacts.

Errors in the specification or utilization of fossil fuel CO₂ emissions within carbon budget or atmospheric CO₂ inverse studies can alias the estimation of biospheric and oceanic carbon exchange. A key component in the simulation of CO₂ concentrations arising from fossil fuel emissions is the spatial distribution of the emission near coastlines. Regridding of fossil fuel CO₂ emissions (FFCO₂) from fine to coarse grids to enable atmospheric transport simulations can give rise to mismatches between the emissions and simulated atmospheric dynamics which differ over land or water. For example, emissions originally emanating from the land are emitted from a grid cell for which the vertical mixing reflects the roughness and/or surface energy exchange of an ocean surface. We test this potential "dynamical inconsistency" by examining simulated global atmospheric CO₂ concentration driven by two different approaches to regridding fossil fuel CO₂ emissions. The two approaches are as follows: (1) a commonly used method that allocates emissions to grid cells with no attempt to ensure dynamical consistency with atmospheric transport and (2) an improved method that reallocates emissions to grid cells to ensure dynamically consistent results. Results show large spatial and temporal differences in the simulated CO₂ concentration when comparing these two approaches. The emissions difference ranges from −30.3 TgC grid cell^-1 yr^-1 (−3.39 kgC m^-2 yr^-1) to +30.0 TgC grid cell^-1 yr^-1 (+2.6 kgC m^-2 yr^-1) along coastal margins. Maximum simulated annual mean CO₂ concentration differences at the surface exceed ±6 ppm at various locations and times. Examination of the current CO₂ monitoring locations during the local afternoon, consistent with inversion modeling system sampling and measurement protocols, finds maximum hourly differences at 38 stations exceed ±0.10 ppm with individual station differences exceeding −32 ppm. The differences implied by not accounting for this dynamical consistency problem are largest at monitoring sites proximal to large coastal urban areas and point sources. These results suggest that studies comparing simulated to observed atmospheric CO₂ concentration, such as atmospheric CO₂ inversions, must take measures to correct for this potential problem and ensure flux and dynamical consistency.

We produced a geologic map of the Av-9 Numisia quadrangle of asteroid Vesta using Dawn spacecraft data to serve as a tool to understand the geologic relations of surface features in this region. These features include the plateau Vestalia Terra, a hill named Brumalia Tholus, and an unusual “dark ribbon” material crossing the majority of the map area. Stratigraphic relations suggest that Vestalia Terra is one of the oldest features on Vesta, despite a model crater age date similar to that of much of the surface of the asteroid. Cornelia, Numisia and Drusilla craters reveal bright and dark material in their walls, and both Cornelia and Numisia have smooth and pitted terrains on their floors suggestive of the release of volatiles during or shortly after the impacts that formed these craters. Cornelia, Fabia and Teia craters have extensive bright ejecta lobes. While diogenitic material has been identified in association with the bright Teia and Fabia ejecta, hydroxyl has been detected in the dark material within Cornelia, Numisia and Drusilla. Three large pit crater chains appear in the map area, with an orientation similar to the equatorial troughs that cut the majority of Vesta. Analysis of these features has led to several interpretations of the geological history of the region. Vestalia Terra appears to be mechanically stronger than the rest of Vesta. Brumalia Tholus may be the surface representation of a dike-fed laccolith. The dark ribbon feature is proposed to represent a long-runout ejecta flow from Drusilla crater.

The purpose of this paper is to introduce the Geologic Mapping of Vesta Special Issue/Section of Icarus, which includes several papers containing geologic maps of the surface of Vesta made to support data analysis conducted by the Dawn Science Team during the Vesta Encounter (July 2011–September 2012). In this paper we briefly discuss pre-Dawn knowledge of Vesta, provide the goals of our geologic mapping campaign, discuss the methodologies and materials used for geologic mapping, review the global geologic context of Vesta, discuss the challenges of mapping the geology of Vesta as a small airless body, and describe the content of the papers in this Special Issue/Section. We conclude with a discussion of lessons learned from our quadrangle-based mapping effort and provide recommendations for conducting mapping campaigns as part of planetary spacecraft nominal missions.

Vesta is a unique, intermediate class of rocky body in the Solar System, between terrestrial planets and small asteroids, because of its size (average radius of ∼263 km) and differentiation, with a crust, mantle and core. Vesta’s low surface gravity (0.25 m/s²) has led to the continual absence of a protective atmosphere and consequently impact cratering and impact-related processes are prevalent. Previous work has shown that the formation of the Rheasilvia impact basin induced the equatorial Divalia Fossae, whereas the formation of the Veneneia impact basin induced the northern Saturnalia Fossae. Expanding upon this earlier work, we conducted photogeologic mapping of the Saturnalia Fossae, adjacent structures and geomorphic units in two of Vesta’s northern quadrangles: Caparronia and Domitia. Our work indicates that impact processes created and/or modified all mapped structures and geomorphic units. The mapped units, ordered from oldest to youngest age based mainly on cross-cutting relationships, are: (1) Vestalia Terra unit, (2) cratered highlands unit, (3) Saturnalia Fossae trough unit, (4) Saturnalia Fossae cratered unit, (5) undifferentiated ejecta unit, (6) dark lobate unit, (7) dark crater ray unit and (8) lobate crater unit. The Saturnalia Fossae consist of five separate structures: Saturnalia Fossa A is the largest (maximum width of ∼43 km) and is interpreted as a graben, whereas Saturnalia Fossa B-E are smaller (maximum width of ∼15 km) and are interpreted as half grabens formed by synthetic faults. Smaller, second-order structures (maximum width of <1 km) are distinguished from the Saturnalia Fossae, a first-order structure, by the use of the general descriptive term ‘adjacent structures’, which encompasses minor ridges, grooves and crater chains. For classification purposes, the general descriptive term ‘minor ridges’ characterizes ridges that are not part of the Saturnalia Fossae and are an order of magnitude smaller (maximum width of <1 km vs. maximum width of ∼43 km). Shear deformation resulting from the large-scale (diameter of <100 km) Rheasilvia impact is proposed to form minor ridges (∼2 km to ∼25 km in length), which are interpreted as the surface expression of thrust faults, as well as grooves (∼3 km to ∼25 km in length) and pit crater chains (∼1 km to ∼25 km in length), which are interpreted as the surface expression of extension fractures and/or dilational normal faults. Secondary crater material, ejected from small-scale and medium-scale impacts (diameters of <100 km), are interpreted to form ejecta ray systems of grooves and crater chains by bouncing and scouring across the surface. Furthermore, seismic shaking, also resulting from small-scale and medium-scale impacts, is interpreted to form minor ridges because seismic shaking induces flow of regolith, which subsequently accumulates as minor ridges that are roughly parallel to the regional slope. In this work we expand upon the link between impact processes and structural features on Vesta by presenting findings of a photogeologic, structural mapping study which highlights how impact cratering and impact-related processes are expressed on this unique, intermediate Solar System body.

We report on a preliminary global geologic map of Vesta, based on data from the Dawn spacecraft’s High-Altitude Mapping Orbit (HAMO) and informed by Low-Altitude Mapping Orbit (LAMO) data. This map is part of an iterative mapping effort; the geologic map has been refined with each improvement in resolution. Vesta has a heavily-cratered surface, with large craters evident in numerous locations. The south pole is dominated by an impact structure identified before Dawn’s arrival. Two large impact structures have been resolved: the younger, larger Rheasilvia structure, and the older, more degraded Veneneia structure. The surface is also characterized by a system of deep, globe-girdling equatorial troughs and ridges, as well as an older system of troughs and ridges to the north. Troughs and ridges are also evident cutting across, and spiraling arcuately from, the Rheasilvia central mound.

However, no volcanic features have been unequivocally identified. Vesta can be divided very broadly into three terrains: heavily-cratered terrain; ridge-and-trough terrain (equatorial and northern); and terrain associated with the Rheasilvia crater. Localized features include bright and dark material and ejecta (some defined specifically by color); lobate deposits; and mass-wasting materials. No obvious volcanic features are evident. Stratigraphy of Vesta’s geologic units suggests a history in which formation of a primary crust was followed by the formation of impact craters, including Veneneia and the associated Saturnalia Fossae unit. Formation of Rheasilvia followed, along with associated structural deformation that shaped the Divalia Fossae ridge-and-trough unit at the equator. Subsequent impacts and mass wasting events subdued impact craters, rims and portions of ridge-and-trough sets, and formed slumps and landslides, especially within crater floors and along crater rims and scarps. Subsequent to the formation of Rheasilvia, discontinuous low-albedo deposits formed or were emplaced; these lie stratigraphically above the equatorial ridges that likely were formed by Rheasilvia. The last features to be formed were craters with bright rays and other surface mantling deposits.

Executed progressively throughout data acquisition, the iterative mapping process provided the team with geologic proto-units in a timely manner. However, interpretation of the resulting map was hampered by the necessity to provide the team with a standard nomenclature and symbology early in the process. With regard to mapping and interpreting units, the mapping process was hindered by the lack of calibrated mineralogic information. Topography and shadow played an important role in discriminating features and terrains, especially in the early stages of data acquisition.

We studied high-resolution images of asteroid Vesta's surface (~70 and 20–25 m/pixel) obtained during the High- and Low-Altitude Mapping Orbits (HAMO, LAMO) of NASA's Dawn mission to assess the formation mechanisms responsible for a variety of lobate, flow-like features observed across the surface. We searched for evidence of volcanic flows, based on prior mathematical modeling and the well-known basaltic nature of Vesta's crust, but no unequivocal morphologic evidence of ancient volcanic activity has thus far been identified. Rather, we find that all lobate, flow-like features on Vesta appear to be related either to impact or erosional processes. Morphologically distinct lobate features occur in and around impact craters, and most of these are interpreted as impact ejecta flows, or possibly flows of impact melt. Estimates of melt production from numerical models and scaling laws suggests that large craters like Marcia (~60 km diameter) could have potentially produced impact melt volumes ranging from tens of millions of cubic meters to a few tens of cubic kilometers, which are relatively small volumes compared to similar-sized lunar craters, but which are consistent with putative impact melt features observed in Dawn images. There are also examples of lobate flows that trend downhill both inside and outside of crater rims and basin scarps, which are interpreted as the result of gravity-driven mass movements (slumps and landslides).

In this paper we present a time-stratigraphic scheme and geologic time scale for the protoplanet Vesta, based on global geologic mapping and other analyses of NASA Dawn spacecraft data, complemented by insights gained from laboratory studies of howardite–eucrite–diogenite (HED) meteorites and geophysical modeling. On the basis of prominent impact structures and their associated deposits, we propose a time scale for Vesta that consists of four geologic time periods: Pre-Veneneian, Veneneian, Rheasilvian, and Marcian. The Pre-Veneneian Period covers the time from the formation of Vesta up to the Veneneia impact event, from 4.6 Ga to >2.1 Ga (using the asteroid flux-derived chronology system) or from 4.6 Ga to 3.7 Ga (under the lunar-derived chronology system). The Veneneian Period covers the time span between the Veneneia and Rheasilvia impact events, from >2.1 to 1 Ga (asteroid flux-derived chronology) or from 3.7 to 3.5 Ga (lunar-derived chronology), respectively. The Rheasilvian Period covers the time span between the Rheasilvia and Marcia impact events, and the Marcian Period covers the time between the Marcia impact event until the present. The age of the Marcia impact is still uncertain, but our current best estimates from crater counts of the ejecta blanket suggest an age between ∼120 and 390 Ma, depending upon choice of chronology system used. Regardless, the Marcia impact represents the youngest major geologic event on Vesta. Our proposed four-period geologic time scale for Vesta is, to a first order, comparable to those developed for other airless terrestrial bodies.