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At least 595 records · Page 33

Extensive Liquid Meltwater Storage in Firn Within the Greenland Ice Sheet

The accelerating loss of mass from the Greenland ice sheet is a major contribution to current sea level rise. Increased melt water runoff is responsible for half of Greenlands mass loss increase. Surface melt has been increasing in extent and intensity, setting a record for surface area melt and runoff in 2012. The mechanisms and timescales involved in allowing surface melt water to reach the ocean where it can contribute to sea level rise are poorly understood. The potential capacity to store this water in liquid or frozen form in the firn (multi-year snow layer) is significant, and could delay its sea-level contribution. Here we describe direct observation of water within a perennial firn aquifer persisting throughout the winter in the southern ice sheet,where snow accumulation and melt rates are high. This represents a previously unknown storagemode for water within the ice sheet. Ice cores, groundairborne radar and a regional climatemodel are used to estimate aquifer area (70 plue or minus 10 x 10(exp 3) square kilometers ) and water table depth (5-50 m). The perennial firn aquifer represents a new glacier facies to be considered 29 in future ice sheet mass 30 and energy budget calculations.

meltwater↗

Principal sources and dispersal patterns of suspended particulate matter in nearshore surface waters of the northeast Pacific Ocean

The author has identified the following significant results. Release-recovery paths of drift cards released in conjunction with ERTS-1 overflight show that nearshore surface currents along the central and northern California coast flowed southward at an average rate in excess of 10 cm/sec (8.5 km/day) during August and September 1973 (California Current). By the middle of October 1973, the nearshore surface currents had reversed and the dominant flow velocity was northward at an average rate in excess of 20 cm/sec (17 km/ day) (Davidson Current). The August-September data suggested the presence of counterclockwise gyres in Monterey Bay and the Gulf of the Farallones, but by the middle of October, the gyres were no longer evident. Imagery of April 1973 showed well developed plumes of suspended sediment in Monterey Bay from the Salinas River and in the Gulf of the Farallones from San Francisco Bay. ERTS-1 imagery provides an effective means of monitoring timber harvest in the redwood forest along the northern California coast. ERTS-1 imagery also clearly portrays contrasting topographic belts characterized by fluvial erosion and by mass movement. The most visually apparent and most persistent river mouth suspended sediment plumes are associated with those rivers that drain belts of topography that appear to have been eroded primarily by mass movement.

Carlson, P. R.↗

Artemis Internal Science Team Update: Deployed Payloads

Artemis will reestablish human presence on the Moon and lead to a new era of scientific discovery and exploration. Led by the National Aeronautics and Space Administration (NASA), the Artemis effort includes a collaboration of space agencies and companies from around the world. In support of Artemis, a cross-disciplinary effort of science, engineering, operations, and human factors personnel is currently developing the best methods, facilities, and field locations to test hardware, train astronauts, and evaluate concepts of operations. This poster, as part of the Artemis Internal Science Team (AIST), provides an update to NASA’s plans for the solicitation, development, and operations of deployed surface payloads. In calendar year 2023, NASA’s Science Mission Directorate will solicit proposals for instruments to be deployed by crew on the surface of the Moon (Fig. 1), beginning with Artemis III. The Artemis III mission will land in the south polar region of the Moon, within 6º of latitude from the south pole, in the vicinity of both persistently illuminated and permanently shadowed areas of the Moon, with potential access to surface-accessible volatile deposits. Several of the proposed landing regions are located among some of the oldest parts of the Moon, and together with the permanently shadowed regions, provide the opportunity to learn about the history of the Moon through previously unexplored lunar regions. Deployed payloads will be a critical part of a notional program that captures the highest-priority science for Artemis III and provides the greatest feed-forward to follow-on missions and the build-up to the Artemis Base Camp.

R. C. Weber↗

Sea Surface Salinity Reemergence in an Updated North Atlantic In Situ Salinity Dataset

Monthly sea surface salinity (SSS) fields are constructed from observations, using objective mapping on a 1° x 1° grid in the Atlantic between 30°S and 50°N in the 1970-2016 period in an update of the dataset of Reverdin et al. Data coverage is heterogeneous, with increased density in 2002 when Argo floats become available, high density along Voluntary Observing Ship lines, and low density south of 10°S. Using lag correlation, the seasonal reemergence of SSS anomalies is investigated between 20° and 50°N in 5° x 5° boxes during the 1993-2016 period, both locally and remotely following the displacements of the deep mixed-layer waters estimated from virtual float trajectories derived from the daily AVISO surface geostrophic currents. Although SSS data are noisy, local SSS reemergence is detected in about half of the boxes, notably in the northeast and southeast, while little reemergence is seen in the central and part of the eastern subtropical gyre. In the same period, sea surface temperature (SST) reemergence is found only slightly more frequently, reflecting the short data duration. However, taking geostrophic advection into account degrades the detection of remote SSS and even SST reemergence. When anomalies are averaged over broader areas, robust evidence of a second and third SSS reemergence peak is found in the northeastern and southeastern parts of the domain, indicating long cold-season persistence of large-scale SSS anomalies, while only a first SST reemergence is seen. Finally, an oceanic reanalysis is used to confirm that the correlation analysis indeed reflects the reemergence of subsurface salinity anomalies.

54 ENVIRONMENTAL SCIENCES↗

Observed changes in hydroclimate attributed to human forcing

Observational and modeling studies indicate significant changes in the global hydroclimate in the twentieth and early twenty-first centuries due to anthropogenic climate change. In this review, we analyze the recent literature on the observed changes in hydroclimate attributable to anthropogenic forcing, the physical and biological mechanisms underlying those changes, and the advantages and limitations of current detection and attribution methods. Changes in the magnitude and spatial patterns of precipitation minus evaporation (P–E) are consistent with increased water vapor content driven by higher temperatures. While thermodynamics explains most of the observed changes, the contribution of dynamics is not yet well constrained, especially at regional and local scales, due to limitations in observations and climate models. Anthropogenic climate change has also increased the severity and likelihood of contemporaneous droughts in southwestern North America, southwestern South America, the Mediterranean, and the Caribbean. An increased frequency of extreme precipitation events and shifts in phenology has also been attributed to anthropogenic climate change. While considerable uncertainties persist on the role of plant physiology in modulating hydroclimate and vice versa, emerging evidence indicates that increased canopy water demand and longer growing seasons negate the water-saving effects from increased water-use efficiency.

54 ENVIRONMENTAL SCIENCES↗

Separating the Influence of Environment from Stress Relaxation Effects on Dwell Fatigue Crack Growth in a Nickel-Base Disk Alloy

Both environmental embrittlement and crack tip visco-plastic stress relaxation play a significant role in determining the dwell fatigue crack growth (DFCG) resistance of nickel-based disk superalloys. In the current study performed on the Low Solvus High Refractory (LSHR) disk alloy, the influence of these two mechanisms were separated so that the effects of each could be quantified and modeled. Seven different microstructural variations of LSHR were produced by controlling the cooling rate and the subsequent aging and thermal exposure heat treatments. Through cyclic fatigue crack growth testing performed both in air and vacuum, it was established that four out of the seven LSHR heat treatments evaluated, possessed similar intrinsic environmental resistance to cyclic crack growth. For these four heat treatments, it was further shown that the large differences in dwell crack growth behavior which still persisted, were related to their measured stress relaxation behavior. The apparent differences in their dwell crack growth resistance were attributed to the inability of the standard linear elastic fracture mechanics (LEFM) stress intensity parameter to account for visco-plastic behavior. Crack tip stress relaxation controls the magnitude of the remaining local tensile stresses which are directly related to the measured dwell crack growth rates. It was hypothesized that the environmentally weakened grain boundary crack tip regions fail during the dwells when their strength is exceeded by the remaining local crack tip tensile stresses. It was shown that the classical creep crack growth mechanisms such as grain boundary sliding did not contribute to crack growth, but the local visco-plastic behavior still plays a very significant role by determining the crack tip tensile stress field which controls the dwell crack growth behavior. To account for the influence of the visco-plastic behavior on the crack tip stress field, an empirical modification to the LEFM stress intensity parameter, Kmax, was developed by incorporating into the formulation the remaining stress level concept as measured by simple stress relaxation tests. The newly proposed parameter, Ksrf, did an excellent job in correlating the dwell crack growth rates for the four heat treatments which were shown to have similar intrinsic environmental cyclic fatigue crack growth resistance.

Dwell crack growth↗

Artemis Internal Science Team Update: Deployed Payloads

Artemis will reestablish human presence on the Moon and lead to a new era of scientific discovery and exploration. Led by the National Aeronautics and Space Administration (NASA), the Artemis effort includes a collaboration of space agencies and companies from around the world [1]. In support of Artemis, a cross-disciplinary effort of science, engineering, operations, and human factors personnel is currently developing the best methods, facilities, and field locations to test hardware, train astronauts, and evaluate concepts of operations. This abstract, as part of the Artemis Internal Science Team (AIST) [2], provides an update to NASA’s plans for the solicitation, development, and operations of deployed surface payloads. In calendar year 2023, NASA’s Science Mission Directorate will solicit proposals for instruments to be deployed by crew on the surface of the Moon (Fig. 1), beginning with Artemis III [3]. The Artemis III mission will land in the south polar region of the Moon, within 6º of latitude from the south pole, in the vicinity of both persistently illuminated and permanently shadowed areas of the Moon, with potential access to surface-accessible volatile deposits [4]. Several of the proposed landing regions are located among some of the oldest parts of the Moon, and together with the permanently shadowed regions, provide the opportunity to learn about the history of the Moon through previously unexplored lunar regions [5]. Deployed payloads will be a critical part of a notional program that captures the highest-priority science for Artemis III and provides the greatest feedforward to follow-on missions and the build-up to the Artemis Base Camp

R. C. Weber↗

Observed Changes in Hydroclimate Attributed to Human Forcing

Observational and modeling studies indicate significant changes in the global hydroclimate in the twentieth and early twenty-first centuries due to anthropogenic climate change. In this review, we analyze the recent literature on the observed changes in hydroclimate attributable to anthropogenic forcing, the physical and biological mechanisms underlying those changes, and the advantages and limitations of current detection and attribution methods. Changes in the magnitude and spatial patterns of precipitation minus evaporation ( P–E ) are consistent with increased water vapor content driven by higher temperatures. While thermodynamics explains most of the observed changes, the contribution of dynamics is not yet well constrained, especially at regional and local scales, due to limitations in observations and climate models. Anthropogenic climate change has also increased the severity and likelihood of contemporaneous droughts in southwestern North America, southwestern South America, the Mediterranean, and the Caribbean. An increased frequency of extreme precipitation events and shifts in phenology has also been attributed to anthropogenic climate change. While considerable uncertainties persist on the role of plant physiology in modulating hydroclimate and vice versa, emerging evidence indicates that increased canopy water demand and longer growing seasons negate the water-saving effects from increased water-use efficiency.

Drought↗

Assessment of Precipitation Anomalies in California Using TRMM and MERRA Data

Using modern satellite (Tropical Rainfall Measuring Mission, TRMM, 1998-2014) and reanalysis (Modern-Era Retrospective Analysis for Research and Applications, MERRA, 1979-2015) data, we reassess certain aspects of the precipitation climate in California from the past decades. California has a well-pronounced rain season that peaks in December-February. However, the 95% confidence interval around the climatological precipitation during these months imply that deviations on the order of 60% of the expected amounts are very likely during the most important period of the rain season. While these positive and negative anomalies alternate almost every year and tend to cancel each other, severe multiyear declines of precipitation in California appear on decadal scales. The 1986-1994 decline of precipitation was similar to the current one that started in 2011 and is apparent in the reanalysis data. In terms of accumulated deficits of precipitation, that episode was no less severe than the current one. While El Niño (the warm phase of the El Nino-Southern Oscillation, ENSO) is frequently cited as the natural forcing expected to bring a relief from drought, our assessment is that ENSO has been driving at best only 6% of precipitation variability in California in the past three decades. Using fractional risk analysis of precipitation during typical versus drying periods, we show that the likelihood of losing the most intensive precipitation events drastically increases during the multiyear drying events. Storms delivering up to 50% of the precipitation in California are driven by atmospheric rivers making landfall. However, these phenomena can be suppressed and even blocked by persistent ridges of atmospheric pressure in the northeast Pacific. The reanalysis and satellite data are proven to be reliable to the extent where they yield information on developing conditions and observed precipitation anomalies.

precipitation↗

Bounds on edge shear layer persistence while approaching the density limit

This paper details the theory of edge shear layer collapse as the density approaches the Greenwald density limit. It significantly extends earlier work, which was restricted in applicability. The zonal shear flow screening length is calculated for banana, plateau and Pfirsch–Schluter regimes. Poloidal field scaling persists in the plateau regime. Neoclassical screening and drift wave–zonal flow dynamics are combined in a theory, which is then reduced to a predator–prey model. Zonal noise, due to incoherent mode coupling, is retained. The threshold condition for edge shear layer collapse is computed, and linked to a critical value of the dimensionless parameter ${\rho }_{\mathrm{s}}/\sqrt{{\rho }_{\mathrm{s}\mathrm{c}}{L}_{n}}$. Here ${\rho }_{s}$ is the ion sound radius, ${\rho }_{sc}$ is the zonal flow screening length and ${L}_{n}$ is the equilibrium density scale length. The limiting initial edge density for shear layer collapse is derived and shown to scale favorably with the plasma current. Here, the results are discussed in light of the density limit and Ohmic phenomenology.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Infrared and Passive Microwave Radiometric Sea Surface Temperatures and Their Relationships to Atmospheric Forcing

The current generation of infrared (IR) and passive microwave (MW) satellite sensors provides highly complementary information for monitoring sea surface temperature (SST). On the one hand, infrared sensors provide high resolution and high accuracy but are obscured by clouds. Microwave sensors on the other hand, provide coverage through non-precipitating clouds but have coarser resolution and generally poorer accuracy. Assuming that the satellite SST measurements do not have spatially variable biases, they can be blended combining the merits of both SST products. These factors have motivated recent work in blending the MW and IR data in an attempt to produce high-accuracy SST products with improved coverage in regions with persistent clouds. The primary sources of retrieval uncertainty are, however, different for the two sensors. The main uncertainty in the MW retrievals lies in the effects of wind-induced surface roughness and foam on emissivity, whereas the IR retrievals are more sensitive to the atmospheric water vapor and aerosol content. Average nighttime differences between the products for the month periods of January 1999 and June 2000 are shown. These maps show complex spatial and temporal differences as indicated by the strong spatially coherent features in the product differences and the changes between seasons. Clearly such differences need to be understood and accounted for if the products are to be combined. The overall goals of this project are threefold: (1) To understand the sources of uncertainty in the IR and MW SST retrievals and to characterize the errors affecting the two types of retrieval as a fiction of atmospheric forcing; (2) To demonstrate how representative the temperature difference between the two satellite products is of Delta T; (3) To apply bias adjustments and to device a comprehensive treatment of the behavior of the temperature difference across the oceanic skin layer to determine the best method for blending thermal infrared and passive microwave measurements of SSTs.

Castro, Sandra L.↗

Simulating US Agriculture in a Modern Dust Bowl Drought

Drought-induced agricultural loss is one of the most costly impacts of extreme weather, and without mitigation, climate change is likely to increase the severity and frequency of future droughts. The Dust Bowl of the 1930s was the driest and hottest for agriculture in modern US history. Improvements in farming practices have increased productivity, but yields today are still tightly linked to climate variation and the impacts of a 1930s-type drought on current and future agricultural systems remain unclear. Simulations of biophysical process and empirical models suggest that Dust-Bowl-type droughts today would have unprecedented consequences, with yield losses approx.50% larger than the severe drought of 2012. Damages at these extremes are highly sensitive to temperature, worsening by approx.25% with each degree centigrade of warming. We find that high temperatures can be more damaging than rainfall deficit, and, without adaptation, warmer mid-century temperatures with even average precipitation could lead to maize losses equivalent to the Dust Bowl drought. Warmer temperatures alongside consecutive droughts could make up to 85% of rain-fed maize at risk of changes that may persist for decades. Understanding the interactions of weather extremes and a changing agricultural system is therefore critical to effectively respond to, and minimize, the impacts of the next extreme drought event.

climate change impacts↗

Land Surface Microwave Emissivities Derived from AMSR-E and MODIS Measurements with Advanced Quality Control

A microwave emissivity database has been developed with data from the Advanced Microwave Scanning Radiometer-EOS (AMSR-E) and with ancillary land surface temperature (LST) data from the Moderate Resolution Imaging Spectroradiometer (MODIS) on the same Aqua spacecraft. The primary intended application of the database is to provide surface emissivity constraints in atmospheric and surface property retrieval or assimilation. An additional application is to serve as a dynamic indicator of land surface properties relevant to climate change monitoring. The precision of the emissivity data is estimated to be significantly better than in prior databases from other sensors due to the precise collocation with high-quality MODIS LST data and due to the quality control features of our data analysis system. The accuracy of the emissivities in deserts and semi-arid regions is enhanced by applying, in those regions, a version of the emissivity retrieval algorithm that accounts for the penetration of microwave radiation through dry soil with diurnally varying vertical temperature gradients. These results suggest that this penetration effect is more widespread and more significant to interpretation of passive microwave measurements than had been previously established. Emissivity coverage in areas where persistent cloudiness interferes with the availability of MODIS LST data is achieved using a classification-based method to spread emissivity data from less-cloudy areas that have similar microwave surface properties. Evaluations and analyses of the emissivity products over homogeneous snow-free areas are presented, including application to retrieval of soil temperature profiles. Spatial inhomogeneities are the largest in the vicinity of large water bodies due to the large water/land emissivity contrast and give rise to large apparent temporal variability in the retrieved emissivities when satellite footprint locations vary over time. This issue will be dealt with in the future by including a water fraction correction. Also note that current reliance on the MODIS day-night algorithm as a source of LST limits the coverage of the database in the Polar Regions. We will consider relaxing the current restriction as part of future development.

Moncet, Jean-Luc↗

Linked Open Data in the Global Change Information System (GCIS)

The U.S. Global Change Research Program (http://globalchange.gov) coordinates and integrates federal research on changes in the global environment and their implications for society. The USGCRP is developing a Global Change Information System (GCIS) that will centralize access to data and information related to global change across the U.S. federal government. The first implementation will focus on the 2013 National Climate Assessment (NCA) . (http://assessment.globalchange.gov) The NCA integrates, evaluates, and interprets the findings of the USGCRP; analyzes the effects of global change on the natural environment, agriculture, energy production and use, land and water resources, transportation, human health and welfare, human social systems, and biological diversity; and analyzes current trends in global change, both human-induced and natural, and projects major trends for the subsequent 25 to 100 years. The NCA has received over 500 distinct technical inputs to the process, many of which are reports distilling and synthesizing even more information, coming from thousands of individuals around the federal, state and local governments, academic institutions and non-governmental organizations. The GCIS will present a web-based version of the NCA including annotations linking the findings and content of the NCA with the scientific research, datasets, models, observations, etc. that led to its conclusions. It will use semantic tagging and a linked data approach, assigning globally unique, persistent, resolvable identifiers to all of the related entities and capturing and presenting the relationships between them, both internally and referencing out to other linked data sources and back to agency data centers. The developing W3C PROV Data Model and ontology will be used to capture the provenance trail and present it in both human readable web pages and machine readable formats such as RDF and SPARQL. This will improve visibility into the assessment process, increase understanding and reproducibility, and ultimately increase credibility and trust of the resulting report. Building on the foundation of the NCA, longer term plans for the GCIS include extending these capabilities throughout the U.S. Global Change Research Program, centralizing access to global change data and information across the thirteen agencies that comprise the program.

Tilmes, Curt A.↗

Carbon budget of the Harvard Forest Long-Term Ecological Research site: pattern, process, and response to global change

How, where, and why carbon (C) moves into and out of an ecosystem through time are long-standing questions in biogeochemistry. Here, we bring together hundreds of thousands of C-cycle observations at the Harvard Forest in central Massachusetts, USA, a mid-latitude landscape dominated by 80–120-yr-old closed-canopy forests. These data answered four questions: (1) where and how much C is presently stored in dominant forest types; (2) what are current rates of C accrual and loss; (3) what biotic and abiotic factors contribute to variability in these rates; and (4) how has climate change affected the forest’s C cycle? Harvard Forest is an active C sink resulting from forest regrowth following land abandonment. Soil and tree biomass comprise nearly equal portions of existing C stocks. Net primary production (NPP) averaged 680–750 g C·m –2 ·yr –1 ; belowground NPP contributed 38–47% of the total, but with large uncertainty. Mineral soil C measured in the same inventory plots in 1992 and 2013 was too heterogeneous to detect change in soil-C pools; however, radiocarbon data suggest a small but persistent sink of 10–30 g C·m –2 ·yr –1 . Net ecosystem production (NEP) in hardwood stands averaged ~300 g C·m –2 ·yr –1 . NEP in hemlock-dominated forests averaged ~450 g C·m –2 ·yr –1 until infestation by the hemlock woolly adelgid turned these stands into a net C source. Since 2000, NPP has increased by 26%. For the period 1992–2015, NEP increased 93%. The increase in mean annual temperature and growing season length alone accounted for ~30% of the increase in productivity. Interannual variations in GPP and NEP were also correlated with increases in red oak biomass, forest leaf area, and canopy-scale light-use efficiency. Compared to long-term global change experiments at the Harvard Forest, the C sink in regrowing biomass equaled or exceeded C cycle modifications imposed by soil warming, N saturation, and hemlock removal. Furthermore, the results of this synthesis and comparison to simulation models suggest that forests across the region are likely to accrue C for decades to come but may be disrupted if the frequency or severity of biotic and abiotic disturbances increases.

54 ENVIRONMENTAL SCIENCES↗

Stream and ocean hydrodynamics mediate partial migration strategies in an amphidromous Hawaiian goby

Abstract Partial migration strategies, in which some individuals migrate but others do not, are widely observed in populations of migratory animals. Such patterns could arise via variation in migratory behaviors made by individual animals, via genetic variation in migratory predisposition, or simply by variation in migration opportunities mediated by environmental conditions. Here we use spatiotemporal variation in partial migration across populations of an amphidromous Hawaiian goby to test whether stream or ocean conditions favor completing its life cycle entirely within freshwater streams rather than undergoing an oceanic larval migration. Across 35 watersheds, microchemical analysis of otoliths revealed that most adult Awaous stamineus were freshwater residents (62% of n = 316 in 2009, 83% of n = 274 in 2011), but we found considerable variation among watersheds. We then tested the hypothesis that the prevalence of freshwater residency increases with the stability of stream flows and decreases with the availability of dispersal pathways arising from ocean hydrodynamics. We found that streams with low variation of daily discharge were home to a higher incidence of freshwater residents in each survey year. The magnitude of the shift in freshwater residency between survey years was positively associated with predicted interannual variability in the success of larval settlement in streams on each island based on passive drift in ocean currents. We built on these findings by developing a theoretical model of goby life history to further evaluate whether mediation of migration outcomes by stream and ocean hydrodynamics could be sufficient to explain the range of partial migration frequency observed across populations. The model illustrates that the proportion of larvae entering the ocean and differential survival of freshwater‐resident versus ocean‐going larvae are plausible mechanisms for range‐wide shifts in migration strategies. Thus, we propose that hydrologic variation in both ocean and stream environments contributes to spatiotemporal variation in the prevalence of migration phenotypes in A. stamineus . Our empirical and theoretical results suggest that the capacity for partial migration could enhance the persistence of metapopulations of diadromous fish when confronted with variable ocean and stream conditions.

54 ENVIRONMENTAL SCIENCES↗

Contemporary income inequality outweighs historic redlining in shaping intra-urban heat disparities in Los Angeles

The roots of intra-urban heat disparity in the U.S. often trace back to historical discriminatory practices, such as redlining, which categorized neighborhoods by race or ethnicity. In this study, we compare the relative impacts of historic redlining and current income inequality on thermal disparities in Los Angeles. A key innovation of our work is the use of land surface temperature data from the ECOSTRESS instrument aboard the International Space Station, enabling us to capture diurnal trends in urban thermal disparities. Our findings reveal that present-day income inequality is a stronger predictor of heat burden than the legacy of redlining. Additionally, land surface temperature disparities exhibit a seasonal hysteresis effect, intensifying during extreme heat events by 5−7 °C. Sociodemographic analysis highlights that African-American and Hispanic populations in historically and economically disadvantaged areas are often the most vulnerable. Our findings suggest that while the legacy of redlining may persist, the present-day heat disparities are not necessarily an immutable inheritance, where targeted investments and interventions can pave the way for a more thermally just future for these communities.

54 ENVIRONMENTAL SCIENCES↗

Evidence that Criegee intermediates drive autoxidation in unsaturated lipids

Significance Autoxidation leads to the slow persistent destruction of organic molecules causing oxidative stress and associated disease. The prevailing autoxidation mechanism of unsaturated lipids involves chain reactions initiated and propagated by H-atom abstraction, mediated by peroxy radicals and other reactive oxygen species. Here we report experimental evidence for an autoxidation mechanism initiated by OH, which is unanticipated and proceeds by OH addition followed by pathways involving Criegee intermediates (CIs). Although CIs are routinely encountered in atmospheric and synthetic organic chemistry, their role in autoxidation is unexpected. Our results suggest that in all likelihood these exotic species play a much more prominent and general role in the chemistry of cells, food, petrochemicals, and the environment beyond what is currently believed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗