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At least 145 records · Page 8

Enhanced Optical Contrast and Switching in Near‐Infrared Electrochromic Devices by Optimizing Conjugated Polymer Oligo(Ethylene Glycol) Sidechain Content and Gel Electrolyte Composition

Abstract A detailed investigation addressing the effects of functionalizing conjugated polymers with oligo(ethylene glycol) (EG n ) sidechains on the performance and polymer‐electrolyte compatibility of electrochromic devices (ECDs) is reported. The electrochemistry for a series of donor‐acceptor copolymers having near‐infrared (NIR)‐optical absorption, where the donor fragment is 3,4‐ethylenedioxythiophene (EDOT) or an EG n functionalized bithiophene (g2T) and the acceptor fragment is diketopyrrolopyrrole (DPP) functionalized with branched alkyl or EG n sidechains, is extensively probed. ECDs are next fabricated and it is found that EG n sidechain incorporation must be finely balanced to promote polymer‐electrolyte compatibility and provide efficient ion exchange. Proper electrolyte‐cation pairing and polymer structural tuning affords a 2x increase in optical contrast (from 12% to 24%) and >60x reduction in switching time (from 20 to 0.3 s). Atomic force microscopy (AFM)/grazing incidence wide‐angle X‐ray scattering (GIWAXS) characterization of the polymer film morphology/microstructure reveals that an over‐abundance of EG n sidechains generates large polymer crystallites, which can suppress ion exchange. Lastly, time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) indicates sidechain/electrolyte identity does not influence the electrolyte penetration depth into the films, and EG n sidechain inclusion increases electrolyte cation uptake. The material structural design insight and guidelines regarding the polymer‐electrolyte ion insertion/expulsion dynamics reported here should be of significant utility for developing next‐generation mixed ionic‐electronic conducting materials.

Chemistry↗

Conservative solute transport processes and associated transient storage mechanisms: Comparing streams with contrasting channel morphologies, land use and land cover

Abstract Land use within a watershed impacts stream channel morphology and hydrology and, therefore, in‐stream solute transport processes and associated transient storage mechanisms. This study evaluated transport processes in two contrasting stream sites where channel morphology was influenced by the surrounding land use, land cover, climate and geologic controls: Como Creek, CO, a relatively undisturbed, high gradient, forested stream with a gravel bed and complex channel morphology, and Clear Creek, IA, an incised, low‐gradient stream with low‐permeability substrate draining an agricultural landscape. We performed conservative stream tracer injections at these sites to address the following questions: (1) How does solute transport vary between streams with differing morphologies? and (2) How does solute transport at each stream site change as a function of discharge? We analysed in‐stream tracer time series data and compared results quantifying solute attenuation in surface and subsurface transient storage zones. Significant trends were observed in these metrics with varying discharge conditions at the forested site but not at the agricultural site. There was a broad range of transport mechanisms and evidence of substantial exchange with both surface and hyporheic transient storage in the relatively undisturbed, forested stream. Changing discharge conditions activated or deactivated different solute transport mechanisms in the forested site and greatly impacted advective travel time. Conversely in the simplified agricultural stream, there was a narrow range of solute transport behaviour across flows and predominantly surface transient storage at all measured discharge conditions. These results demonstrate how channel simplification inhibits available solute transport mechanisms across varying discharge conditions.

54 ENVIRONMENTAL SCIENCES↗

Coupled primary production and respiration in a large river contrasts with smaller rivers and streams

Abstract Although time series in ecosystem metabolism are well characterized in small and medium rivers, patterns in the world's largest rivers are almost unknown. Large rivers present technical difficulties, including depth measurements, gas exchange (, ) estimates, and the presence of large dams, which can supersaturate gases. We estimated reach‐scale metabolism for the Hanford Reach of the Columbia River (Washington state, USA), a free‐flowing stretch with an average discharge of 3173 . We calculated from semi‐empirical models and directly estimated it from tracer measurements. We fixed at the median value from these calculations (0.5 ), and used maximum likelihood to estimate reach‐scale, open‐channel metabolism. Both gross primary production (GPP) and ecosystem respiration (ER) were high (GPP range: 0.3–30.8 g , ER range: 0.8–30.6 g ), with peak GPP and ER occurring in the late summer or early fall. GPP increased exponentially with temperature, consistent with metabolic theory, while light was seasonally saturating. Annual average GPP, estimated at 1500 g carbon , was in the top 2% of estimates for other rivers. GPP and ER were tightly coupled and 90% of GPP was immediately respired, resulting in net ecosystem production near 0. Patterns in the Hanford Reach contrast with those in small‐medium rivers, suggesting that metabolism magnitudes and patterns in large rivers may not be simply scaled from knowledge of smaller rivers.

54 ENVIRONMENTAL SCIENCES↗

Trace metal contents of autotrophic flagellates from contrasting open‐ocean ecosystems

Abstract Nano‐ and picophytoplankton are a major component of open‐ocean ecosystems and one of the main plankton functional types in biogeochemical models, yet little is known about their trace metal contents. In cultures of the picoeukaryote Ostreococcus lucimarinus , iron limitation reduced iron quotas by 68%, a fraction of the plasticity known in diatoms. In contrast, a commonly co‐occurring cyanobacterium, Prochlorococcus , showed variable iron contents with iron availability in culture. Synchrotron X‐ray fluorescence was used to measure single‐cell metal (Mn, Fe, Co, Ni, Zn) quotas of autotrophic flagellates (1.4–16.8‐ μ m diameter) collected from four ocean regions. Iron quotas were tightly constrained and showed little response to iron availability, similar to cultured Ostreococcus . Zinc quotas also did not vary with zinc availability but appeared to vary with phosphorus availability. These results suggest that macronutrient and metal availability may be equally important for controlling metal contents of small eukaryotic open‐ocean phytoplankton.

54 ENVIRONMENTAL SCIENCES↗

X-ray Phase Contrast Imaging of the Impact of Multiple HMX Particles in a Polymeric Matrix

The initiation of high explosives (HEs) under shock loading lacks a comprehensive understanding: particularly at the particle scale. One common explanation is the hot spot theory, which suggests that energy in the material resulting from the impact event is localized in a small area causing an increase in temperature that can lead to ignition. This study focuses on the response of HMX particles (a common HE) within a polymer matrix (Sylgard-184 (R)), a simplified example of a polymer-bound explosive (PBX). These PBXs consist of multiple HMX particles in a single polymer-bound sample. A light gas gun was used to load the samples at impact velocities above 400 m/s. The impact events were visualized using X-ray phase-contrast imaging (PCI) allowing real-time observation of the impact event. The experiment used two different types of samples (multi-particle and two crystals) and found evidence of cracking and debonding in both sample types. Additionally, it was found that the multiple particle samples showed similar evidence of damage at lower velocities than that of single particle samples. This is an expected result as the multiple particles add additional interfaces for stress concentration and frictional heating.

42 ENGINEERING↗

Phase Contrast X‐Ray Imaging of the Collapse of an Engineered Void in Single‐Crystal HMX

Abstract Imaging the collapse of a single void that creates a hot spot initiation site in an otherwise defect‐free explosive is challenging given the spatial and temporal scales involved in explosive systems. This work presents our attempt to examine a single hot spot mode (void collapse) in single‐crystal octahydro‐l,3,5,7‐tetranitro‐l,3,5,7‐tetrazocine (HMX) embedded in Sylgard. The hot spot heating mechanisms involved with pore collapse include adiabatic heating, jetting, and viscoplastic dissipation. Quantifying the dynamics of a pore collapse is a crucial step to understanding which mechanisms dominate during ignition events. Our experiments were conducted with a single‐stage, light‐gas gun at Argonne National Laboratory's Advanced Photon Source, applying the phase contrast imaging technique while collecting high‐speed video. The details of HMX single crystal production, defect (pore) engineering, and sample construction, along with experimental results are presented here. These results demonstrate that detailed collapse dynamics can be obtained from homogeneous, single‐crystal explosives with this approach. Qualitative comparisons are made with simulation data which show good agreement in the transition between a quasi‐symmetric pore collapse and an asymmetric collapse with jetting across the pore as measured with normalized pore area and pore circularity.

42 ENGINEERING↗

Invasive intraductal papillary mucinous neoplasms of the pancreas: relationships between mural nodules detected on thin-section contrast-enhanced MDCT and invasive components

Purpose: To elucidate the relationships between mural nodules (MNs) and invasive components in patients with invasive intraductal papillary mucinous neoplasm (IPMN) on the basis of thin-section contrast-enhanced multidetector CT (CE-MDCT) and pathologic findings. Methods: This retrospective study included 28 patients with surgically confirmed invasive IPMN. Two radiologists independently evaluated the thin-section (1-mm section thickness, no overlap) triple-phase CE-MDCT images for MNs, invasive components, and the continuity between them using a five-point scale (confidence scores of 1–3 as negative, 4 and 5 as positive). Kappa statistic was used to evaluate interobserver agreement. The CE-MDCT findings were correlated with pathologic findings. Results: Interobserver agreement was good or excellent. MNs consisting of tumor cells were recognized in 12 (42.9%) of 28 patients with no discrepancy between the two radiologists. Invasive components were detected in 85.7% and 82.1% in the pancreatic parenchymal phase for radiologist 1 and 2, respectively, and recognized as hypoattenuating areas. Pathologic continuities between MNs and invasive components were confirmed in five (41.7%) of 12 patients with MNs and these were detected on CE-MDCT. When combined seven patients without continuities between MNs and invasive components and 16 patients without MNs, the invasive components pathologically derived from non-nodular low-height papillary epithelium in 23 (82.1%) of 28 patients. Conclusions: The invasive components derived more often from low-height papillary epithelium without MN appearance on CE-MDCT than from MN. Careful attention should be paid to the existence of an invasive component even in the absence of an enhancing MN.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Seasonal delay of Sahelian rainfall driven by an east–west contrast in radiative forcing in idealized CESM experiments

Recent studies suggest the observed seasonal delay of rainfall over the Sahel is mainly driven by anthropogenic aerosol forcing, which features a robust east–west contrasting changes in recent decades, with negative and positive top-of-the-atmosphere shortwave radiative forcing in South and East Asia (SA&EA) and in North America and Europe (NA&EU), respectively. Their individual effects on the Sahel rainfall annual cycle remain unclear. Here, by designing idealized sensitivity experiments based on Community Earth System Model (CESM1.2), we show that both negative radiative forcing over SA&EA and positive radiative forcing over NA&EU contribute to the delayed phase and enhanced amplitude of Sahel rainfall annual cycle. To understand the underlying physical processes, both the convective quasi-equilibrium (CQE) and atmospheric energetic frameworks are utilized. Both frameworks can well explain the seasonal delay in the rainfall annual cycle over the Sahel under the regional radiative forcings, with the CQE framework showing stronger explanatory power. Based on the insights from both frameworks, we conducted a moisture budget analysis and found that the negative radiative forcing over SA&EA causes an anomalous low-level anticyclonic circulation, which transports more moisture to the Sahel. As the anomalous anticyclone is stronger in summer and fall compared to spring, rainfall is delayed in the Sahel. Further, under the influence of the positive radiative forcing over NA&EU, more warming in the northern hemisphere causes northward transport of moisture to the northern tropics associated with the cross-equatorial transport of energy. The moisture transport increases relativehumidity over the Sahel and enhances the effective atmospheric heat capacity that delays the seasonal rainfall.

54 ENVIRONMENTAL SCIENCES↗

Contrasting stream nitrate and sulfate response to recovery from experimental watershed acidification

Improvements in air quality have led to ecosystem recovery from acidic deposition, but the mechanisms and trajectories of this recovery are not fully understood. Here, we present long-term stream response and recovery data for paired watersheds at the Bear Brook Watershed in Maine (BBWM) during declining ambient SO 4 and NO 3 in precipitation. East Bear (EB) received ambient deposition from 1989 to 2018; West Bear (WB) received artificially elevated N+S from 1989 to 2016. The WB treatment was discontinued after 2016, the beginning of the recovery from both the experimental N+S and ambient decline. Stream SO 4 in WB gradually declined after the treatment ended, from ~147 µeq L -1 in 2010-16 to ~126 µeq L -1 in 2017-18. The declining S inputs induced desorption of SO 4 from soil phase surfaces, with stream loss far exceeding precipitation input. At the current rate of recovery, it will be many decades before the WB stream returns to pre-treatment SO 4 concentrations. In contrast, NO 3 is only weakly adsorbed in soil, and WB stream NO 3 concentrations rapidly declined from ~39 µeq L -1 in 2010-16 to ~5 µeq L -1 in 2017-18, comparable to the N-limited EB stream. The acid anions are strongly coupled to base cation chemistry in streams, and there was a distinct hysteretic response of Ca and Mg to the chronic acidification, as (Ca+Mg) increased rapidly during the initial years, followed by declining values due to depletion of the soil exchange complex. This 30-year monitoring study (1989-2019) provides insights into recovery mechanisms from acidic deposition and highlights the role of abiotic processes in soil that mediate nutrient cycling and retention. Finally, documenting the rapid response of N alongside the slower recovery for S identifies the temporal resolution necessary for other whole-watershed recovery studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influence of contrasting redox conditions on iron (oxyhydr)oxide transformation and associated phosphate sorption

Iron (oxyhydr)oxides strongly adsorb phosphate and limit its bioavailability, but interactions between phosphate and various Fe (oxyhydr)oxides are poorly constrained in natural systems. An in-situ incubation experiment was conducted to explore Fe (oxyhydr)oxide transformation and effects on phosphate sorption in soils with contrasting saturation and redox conditions. Synthetic Fe (oxyhydr)oxides (ferrihydrite, goethite and hematite) were coated onto quartz sand and either pre-sorbed with phosphate or left phosphate-free. The oxide-coated sands were mixed with natural organic matter, enclosed in mesh bags, and buried in and around a vernal pond for up to 12 weeks. Redox conditions were stable and oxic in the upland soils surrounding the vernal pond but largely shifted from Fe reducing to Fe oxidizing in the lowland soils within the vernal pond as it dried during the summer. Iron (oxyhydr)oxides lost more Fe (- 41% ± 10%) and P (- 43 ± 11%) when incubated in the redox-dynamic lowlands compared to the uplands (- 18% ± 5% Fe and - 24 ± 8% P). Averaged across both uplands and lowlands, Fe losses from crystalline goethite and hematite (- 38% ± 6%) were unexpectedly higher than losses from short range ordered ferrihydrite (- 12% ± 10%). We attribute losses of Fe and associated P from goethite and hematite to colloid detachment and dispersion but losses from ferrihydrite to reductive dissolution. Iron losses were partially offset by retention of solubilized Fe as organic-bound Fe(III). Iron (oxyhydr)oxides that persisted during the incubation retained or even gained P, indicating low amounts of phosphate sorption from solution. In conclusion, these results demonstrate that hydrologic variability and Fe (oxyhydr)oxide mineralogy impact Fe mobilization pathways that may regulate phosphate bioavailability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterizing the microstructures of mammalian enamel by synchrotron phase contrast microCT

The enamel of mammalian teeth is a highly mineralized tissue that must endure a lifetime of cyclic contact and is inspiring the development of next-generation engineering materials. Attempts to implement enamel-inspired structures in synthetic materials have had limited success, largely due to the absence of a detailed understanding of its microstructure. Here, the present work used synchrotron phase-contrast microCT imaging to evaluate the three-dimensional microstructure of enamel from four mammals including Lion, Gray Wolf, Snow Leopard, and Black Bear. Quantitative results of image analysis revealed that the decussation pattern of enamel consists of discrete diazone (D) and parazone (P) bands of rods organized with stacking arrangement of D+/P/D-/P in all mammals evaluated; the D+ and D- refer to distinct diazone bands with juxtaposed rod orientations from the reference plane. Furthermore, the rod orientations in the bands can be described in terms of two principal angles, defined here as the pitch and yaw. While the pitch angle increases from the outer enamel to a maximum (up to ≈ 40°) near the dentin enamel junction, minimal spatial variations are observed in yaw across the enamel thickness. There are clear differences in the decussation parameters of enamel across species that are interpreted here with respect to the structural demands placed on their teeth. The rod pitch and band width of enamel are identified as important design parameters and appear to be correlated with the bite force quotient of the four mammals evaluated.

36 MATERIALS SCIENCE↗

Contrasting effects of land-use and local disturbance on plant and pollinator communities in wetlands

While pollinators and wetlands both provide important ecosystem services (e.g., the pollination of flowering plants and improving water quality), the relationship between the two is not well understood. Both biotic and abiotic effects can mediate the local wetland flower and pollinator community. In this study, we investigated how land use, including a land use gradient at five different radii, from 250 m to 2 km, along with anthropogenic disturbance affected pollinators in wetland ecosystems. We surveyed the abundance and diversity of plant-pollinator communities in fifteen different wetlands across two years. We also tested the relationship between water quality and temperature, and the abundance and diversity of flowering plants and pollinating insects. Our results suggest that increasing temperature, which was strongly associated with developed land use, had a negative effect on the floral display of wetland plants, as well as the abundance of all flower visitors and hover flies. Hover fly abundance was also positively associated with agricultural land use and total nitrogen in the water. Meanwhile, the abundance of female bees was affected by an interaction between temperature and disturbance: female bees were most abundant when temperatures were lower in areas of low disturbance. In contrast, pollinator species richness increased with temperature when developed land use was low, and floral diversity was strongly affected by several interactions between disturbance, land use, and water quality. Finally, the community composition of both plants and insects varied significantly among low, medium, and high disturbance categories, with weedier, non-native species being significantly associated with areas of higher disturbance and in sites with greater anthropogenic land use. We demonstrate that ecological communities shift significantly in response to anthropogenic change. Our work also illustrates the importance of quantifying interactions between land use and local disturbance with abiotic factors such as temperature and water quality on ecological systems.

Disturbance↗

Direct observation on supersonic microprojectile penetration of carbon fiber composites with ultrafast synchrotron X-ray phase contrast imaging

High-speed penetration into carbon fiber composites is of fundamental importance to materials science and impact engineering, but research along this line suffers considerably from the lack of direct experimental observations. Here we investigate such penetration dynamics of a unidirectional carbon fiber reinforced epoxy (UCFRE) composite, with a combination of in situ, ultrafast, synchrotron phase contrast imaging and finite element (FE) analysis. The experiments yield the first direct observation on projectile trajectories and fiber-scale deformation and damage in the UCFRE composites during supersonic microprojectile penetration, for different fiber orientations (0 degrees - 90 degrees from the impact direction) and projectile velocities (600 - 850 m.s -1 ), at unprecedented temporal (~ 100 ps) and spatial (5 μm) resolutions. The maximum penetration depth decreases with increasing fiber orientation angles, as a result of anisotropic damage evolution in the composite sample. Strain localizations are prone to develop along a direction perpendicular to the fiber orientation, while the damage or cavity region, along the fiber direction. FE modeling with a three-dimensional Hashin criterion yields consistent projectile trajectory and cavity morphology with the experimental results. Finally, with increasing fiber orientation angles, damage analyses show a transition in the damage mode from fiber compression to matrix compression damage, in line with the increasing maximum penetration depth.

36 MATERIALS SCIENCE↗

Surviving nanoscale interfacial stability in extreme thermal expansion contrast Zn(CN) 2 -epoxy resin matrix composites

Here, we report the remarkable stability at the nanoscale matrix-filler interface in a series of overall low coefficient of thermal expansion (CTE) zinc cyanide (ZC)/epoxy resin composites. These interfaces demonstrate the stability of highly contrasting materials. These composites are designed to optimize the properties of both materials: epoxy resins are valued for their high strength, superb chemical resistance, low dielectric properties, and adhesive abilities. ZC, a model flexible framework, exhibits negative thermal expansion (NTE) behavior and compensates for the epoxy resin’s detrimentally large thermal expansion values. Filled resins minimize the native 65 ppm/°C CTE values to 19 ppm/° C over a wide temperature range while maintaining linearity, yielding composites compatible with typical metal and ceramic substrates’—commonly bonded to the resin— 0–20 ppm/° C CTE values. Additionally, with significant intrinsic differences in the materials, we use wide-angle X-ray diffraction and atomic force microscopy to elucidate thermal movement. The ZC/epoxy interface is surprisingly resilient over 1,000 cycles between -55° C and 75° C, extremes typical to aerospace applications. Further, we show that the resin viscosity remains less than 21 Pa*s at up to 30 vol% ZC, an important consideration for workability. We also discuss settling distribution, glass transition temperature, flexural strength, and longevity. All results point favorably towards practical implementation in low thermal expansion application needs: filling the gap in component design.

42 ENGINEERING↗

High-speed synchrotron X-ray phase-contrast imaging for evaluating microscale damage mechanisms and tracking cracking behaviors inside cross-ply GFRCs

In this study, we integrated the high-speed synchrotron X-ray phase-contrast imaging (PCI) with a modified Kolsky compression bar loading platform to visualize the dynamic failure processes of cross-ply glass fiber reinforced composites (GFRCs). Four S-2 glass/SC-15 composite specimens were prepared, having similar thicknesses but different stacking sequences, namely as [0 12 /90 12 ], [90 12 /0 12 ], [0 8 /90 8 /0 8 ], and [90 8 /0 8 /90 8 ]. Three-dimensional synchrotron X-ray computed tomography and scanning electron microscopy (SEM) were employed to examine the microstructures and quantify the fiber volume fractions. Each specimen was notched and subjected to a dynamic three-point flexural loading. The onset of cracking close to the notch tip, crack propagation in 0° or 90° plies and their interface, crack opening, and ultimately failure of the specimen were captured by high-speed synchrotron X-ray PCI. Additional dynamic experiments were performed to determine the average time when the stress wave propagated through the specimen and correlate the X-ray images with the specimen's force-deflection response. Finally, the surface morphology of each specimen after the dynamic loading was imaged by SEM. Comparison between real-time X-ray images and post-fracture SEM images demonstrated the capability of the X-ray method to record damage evolution inside composites. Furthermore, the high spatial and temporal resolutions of the X-ray setup and edge enhancement by PCI enabled the identification of microscale damage features within 1 μs. Two damaging processes were identified, crack growth was quantified, and fracture toughness of the composites was evaluated. The method is deemed useful to reveal microscale damage mechanisms and track cracking behaviors inside cross-ply GFRCs under dynamic loading in real time.

42 ENGINEERING↗

Contrasting modes of macro and microsynteny evolution in a eukaryotic subphylum

Examination of the changes in order and arrangement of homologous genes is key for understanding the mechanisms of genome evolution in eukaryotes. Previous comparisons between eukaryotic genomes have revealed considerable conservation across species that diverged hundreds of millions of years ago (e.g., vertebrates, bilaterian animals, and filamentous fungi). However, understanding how genome organization evolves within and between eukaryotic major lineages remains underexplored. We analyzed high-quality genomes of 120 representative budding yeast species (subphylum Saccharomycotina) spanning ~400 million years of eukaryotic evolution to examine how their genome organization evolved and to compare it with the evolution of animal and plant genome organization. We, in this study, found that the decay of both macrosynteny (the conservation of homologous chromosomes) and microsynteny (the conservation of local gene content and order) was strongly associated with evolutionary divergence across budding yeast major clades. However, although macrosynteny decayed very fast, within ~100 million years, the microsynteny of many genes—especially genes in metabolic clusters (e.g., in the GAL gene cluster)—was much more deeply conserved both within major clades and across the subphylum. We further found that when genomes with similar evolutionary divergence times were compared, budding yeasts had lower macrosynteny conservation than animals and filamentous fungi but higher conservation than angiosperms. In contrast, budding yeasts had levels of microsynteny conservation on par with mammals, whereas angiosperms exhibited very low conservation. Our results provide new insight into the tempo and mode of the evolution of gene and genome organization across an entire eukaryotic subphylum.

59 BASIC BIOLOGICAL SCIENCES↗

Differences in spore size and atmospheric survival shape stark contrasts in the dispersal dynamics of two closely related fungal pathogens

A frequently ignored but critical aspect of microbial dispersal is survival in the atmosphere. Here, we exposed spores of two closely related, morphologically dissimilar, and economically important fungal pathogens to typical atmospheric environments and modeled their movement in the troposphere. Alternaria solani conidia are nearly 10 times larger than A. alternata conidia, but in our experiments, most died within 24 h, while over half of A. alternata conidia remained viable on day 12. Next, we modeled the movement of spores across North America. We predict 99% of the larger A. solani conidia settle within 24 h, with a maximum dispersal distance of 100 km. By contrast, most A. alternata conidia remain airborne for more than 12 days, and dispersal over long distances(2000 km) is likely. Counterintuitively, the larger A. solani conidia survive poorly, as compared to smaller A. alternata conidia, but also land sooner and move over shorter distances.

59 BASIC BIOLOGICAL SCIENCES↗

Subsoil organo-mineral associations under contrasting climate conditions

Climate differences can induce profound changes in organo-mineral associations in soils. However, the magnitude of these modifications, whether as a direct effect of climate conditions or an indirect effect through changes in soil mineralogy, are still not fully understood. In this study, we aimed to improve understanding of how climate and resultant changes in soil mineralogy affect subsoil (i.e., 0.4–0.9 m) organo-mineral interactions at the macro- and microscale. A set of subsoil samples were collected throughout an elevation gradient (approximately 1800 to 2400 mm precipitation year –1 and 15 to 24ºC) on Kohala Mountain, Hawaii. We carried out a combined approach of bulk soil analyses with mineral extractions and spectroscopic and spectromicroscopic analyses. Significant positive correlations (p < 0.05) between soil organic carbon (SOC) with extracted Fe and Al (dithionite citrate bicarbonate – DCB and ammonium oxalate – OX) at the bulk soil scale supported prior research showing concurrent decline of subsoil Fe, Al and SOC above a precipitation level of ~2000 - ~2200 mm year -1 . However, divergence in microscale organo-mineral associations identified using NanoSIMS allowed us to discern the relative roles of Fe and Al in promoting organo-mineral associations. At the lower precipitation range (~1800 mm year -1 ), the clay fraction < 2 µm showed higher amounts of organic matter (OM) co-localized with Fe & Al compared with the higher precipitation level (~2300 mm year -1 ), where OM was mostly unassociated or only associated with Al. While Fe contributed to approximately 40% of the microscale organo-mineral associations in the lower precipitation site (quantified by co-localizations with OM segments), this contribution at the higher rainfall regime was only 5%. In contrast, the contribution of Al was approximately the same in both rainfall levels (approximately 30%). Therefore, associations with Al may be more important than Fe for OM stabilization under reducing climate conditions. The normalized CN:C ratio based on individual pixels was found to be higher when co-localized with Al, Fe, or both, especially under the high precipitation regime. This fact points towards the importance of Fe and Al to stabilize more N-rich OM, especially at high rainfall levels. In addition, subsoil from higher rainfall conditions exhibited more reduced forms of Fe (assessed by Fe K-edge XANES) and lower proportions of carboxyl-C (5% lower in the relative abundance) as well as higher alkyl/O-alkyl ratios determined by CP-MAS 13C NMR. Such differences in composition may directly influence the organo-mineral associations at both locations, as differences in Fe reduction and the presence of carboxyl-C groups are recognized to play a role in OM stabilization. We conclude that spatial relationships between Fe and Al with SOC at the microscale show a shift towards Al-dominated SOC associations at higher precipitation that could not be ascertained from bulk measurements alone. Therefore, they are of fundamental importance to understand the impact of climate change on SOC stabilization.

54 ENVIRONMENTAL SCIENCES↗