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At least 991 records · Page 55

Identifying hydrologic signatures associated with streamflow depletion caused by groundwater pumping

Abstract Groundwater pumping can reduce streamflow in nearby waterways (‘streamflow depletion’), a process which must be accounted for in integrated management of surface and groundwater resources. However, causal identification of streamflow depletion from hydrographs alone is challenging because pumping impacts are masked by other drivers of hydrologic variability. To identify potential indicators of streamflow depletion, we used synthetic hydrographs and an analytical streamflow depletion model to assess potential pumping impacts on specific hydrograph characteristics (‘hydrologic signatures’) for 215 streamgages spanning the conterminous United States (CONUS). We found that streamflow depletion commonly impacts signatures associated with seasonal and annual low flows and low flow recessions. The largest impacts occurred during dry years, suggesting streamflow depletion may be evident in dry years even where impacts are unmeasurable in wet years. Random forest models indicated that streamflow depletion could significantly impact Annual, Summer, and Fall signatures in most streams. Our finding that multiple hydrologic signatures are consistently responsive to streamflow depletion across CONUS suggests that the underlying hydrological processes linking pumping to streamflow reductions are consistent across diverse settings, information that will aid in identifying indicators of streamflow depletion from streamflow hydrographs.

Lapides, Dana A.↗

Chemometric optimisation of pressurised liquid extraction for the determination of alliin and S‐allyl‐cysteine in giant garlic ( Allium ampeloprasum L.) by liquid chromatography tandem mass spectrometry

Abstract Introduction Giant garlic is a functional food that contains different kinds of bioactive molecules with beneficial effects on chronic noncommunicable diseases like diabetes and cardiovascular conditions. Considering biosynthesis pathways, abundance, and biological activity, alliin and S‐allyl‐cysteine were used as chemical markers of organosulphur compounds present in giant garlic. Objective To establish a chemometric optimisation of pressurised liquid extraction for the determination of alliin and S‐allyl‐cysteine in giant garlic by liquid chromatography tandem mass spectrometry (LC–MS/MS). Methodology Samples were blanched (ca. 90°C for 10 min) to inactivate alliinase and γ‐glutamyl transpeptidase enzymes and then freeze‐dried. Chemometric optimisation was performed via response surface methodology based on central composite design (CCD). Organosulphur compound yields were determined applying a validated LC–MS/MS method in multiple reaction monitoring (MRM) mode using the following transitions: for alliin m/z 178 → 74 and for S‐allyl‐cysteine m/z 162 → 41. Results According to CCD results, under constant conditions of pressure (1500 psi) and time (20 min), the optimal conditions for pressurised liquid extraction of alliin and S‐allyl‐cysteine were 70.75 and 68.97% v/v of ethanol in extraction solvent and 76.45 and 98.88°C as extraction temperature, respectively. Multiple response optimisation for the simultaneous extraction of both organosulphur compounds was established via desirability function. Under these conditions, 2.70 ± 0.27 mg g −1 dry weight (DW) of alliin and 2.79 ± 0.22 mg g −1 DW of S‐allyl‐cysteine were extracted. Conclusions These results clearly demonstrated that pressurised liquid extraction is an efficient green technique to extract bioactive organosulphur compounds from giant garlic. Extraction yields were significantly ( p < 0.05) higher than those obtained with conventional ultra‐turrax extraction.

Peterssen‐Fonseca, Darlene↗

The Sensitivity of PBX 9502 to Drilling Operations

Polymer-bonded explosive (PBX) 9502 (95% TATB, 5% Kel-F 800 by weight) is dry-drilled on a CNC milling machine and its thermomechanical response to varying feed rates, drilling speeds, and peck depths with 4 mm and 5 mm diameter drill bits is investigated. The tested samples are affixed to a force sensor that enables recording temporally resolved cutting forces and torques, and a drill-embedded thermocouple yields local temperature data. From the data, an empirical relationship between temperature changes and feed per revolution is developed, which reveals reduced temperatures in higher feed per revolution regimes for PBX 9502. The observed relationship allows extrapolating to temperatures for other hole diameters, indicating increased temperature for smaller diameter drilling across the board. Additional testing was performed with PBX 9501 (95% HMX, 2.5% Estane®, 2.5% BDNPA/BDNPF by weight), albeit over a reduced parameter space, which revealed the opposite behavior for the feed per revolution temperature dependence. It is concluded that both PBX 9502 and PBX 9501 can be dry-drilled efficiently beyond the limits of presently applicable US-DOE standards, where cutting interface temperatures remain far below material critical temperatures. Finally, data reveals that coolant usage in the drilling process for these materials provides a wide safety margin.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Reduction of Iron‐Ore Pellets Using Different Gas Mixtures and Temperatures

Direct reduction of iron ore (DRI) is gaining an increased attention due to the growing need to decarbonize industrial processes. The current industrial DRI processes are performed using reformed natural gas, which results in CO 2 emission, although it is less than carbothermic reduction in the blast furnace. Carbon‐free reduction may be realized through the utilization of green H 2 as a reducing agent, in place of natural gas. Herein, the effects of various gas mixtures and temperature on the reduction kinetics of the hematite iron‐ore pellets are focused on in this work. Pellets are reduced at 700, 800, 850, and 900 °C in hydrogen and using various gas mixes at 850 °C. Morphology of the pellets is investigated with the help of scanning electron microscopy and mercury intrusion porosimetry. The effects of temperature and gas composition on the reduction kinetics and porosity of the pellets are discussed. A notable effect of reduction rate on the internal structure of the pellets is detected, slower reduction rate yielded bigger pores offsetting the gas composition. Higher temperature results in coarser pores and higher porosity. Finally, increase of CO content in the gas mix also leads to bigger pore size.

36 MATERIALS SCIENCE↗

Within‐field soil moisture variability and time‐invariant spatial structures of agricultural fields in the US Midwest

Abstract Understanding soil moisture variability and estimating high‐resolution soil moisture at subfield to field scales is critical for agricultural research and applications. However, systematic investigation of subfield scale soil moisture variability over cropland is still lacking from both measurement and satellite remote sensing. In this study, we aim to investigate (1) the characteristics of within‐field soil moisture distribution over typical cropland in the US Midwest and (2) the capabilities of satellite remote sensing in capturing the spatiotemporal variabilities of soil moisture at subfield scale. Specifically, we conducted soil moisture field experiments in three typical commercial agricultural fields (∼85 acres per field) in central Illinois, representing typical commercial farmlands in the US Midwest, and compared the soil moisture measurements with satellite remote sensing data from optical and active microwave sensors. In each field, dense soil moisture samples (spaced at 50–60 m) were obtained for two dry down events in May and July 2021, and multiple long‐term soil moisture stations were installed. We found prominent time‐invariant spatial structures of soil moisture at within‐field scales both during the dry down period and over longer time scales, and the stability is minimally affected by plant water use during the growing season. Comparing the field campaign measurements with satellite remote sensing data, we found that surface reflectance of shortwave infrared bands, such as SWIR1 (1610 nm) from Sentinel‐2, can capture relative surface soil moisture patterns at within‐field scales, but their relationships with soil moisture are field specific. These findings and the improved understanding of within‐field soil moisture dynamics could potentially help future research on high‐resolution soil moisture estimation with multi‐source remote sensing data.

Yang, Yi↗

Degradation Reduces Microbial Richness and Alters Microbial Functions in an Australian Peatland

Abstract Peatland ecosystems cover only 3% of the world’s land area; however, they store one-third of the global soil carbon (C). Microbial communities are the main drivers of C decomposition in peatlands, yet we have limited knowledge of their structure and function. While the microbial communities in the Northern Hemisphere peatlands are well documented, we have limited understanding of microbial community composition and function in the Southern Hemisphere peatlands, especially in Australia. We investigated the vertical stratification of prokaryote and fungal communities from Wellington Plains peatland in the Australian Alps. Within the peatland complex, bog peat was sampled from the intact peatland and dried peat from the degraded peatland along a vertical soil depth gradient (i.e., acrotelm, mesotelm, and catotelm). We analyzed the prokaryote and fungal community structure, predicted functional profiles of prokaryotes using PICRUSt, and assigned soil fungal guilds using FUNGuild. We found that the structure and function of prokaryotes were vertically stratified in the intact bog. Soil carbon, manganese, nitrogen, lead, and sodium content best explained the prokaryote composition. Prokaryote richness was significantly higher in the intact bog acrotelm compared to degraded bog acrotelm. Fungal composition remained similar across the soil depth gradient; however, there was a considerable increase in saprotroph abundance and decrease in endophyte abundance along the vertical soil depth gradient. The abundance of saprotrophs and plant pathogens was two-fold higher in the degraded bog acrotelm. Soil manganese and nitrogen content, electrical conductivity, and water table level (cm) best explained the fungal composition. Our results demonstrate that both fungal and prokaryote communities are shaped by soil abiotic factors and that peatland degradation reduces microbial richness and alters microbial functions. Thus, current and future changes to the environmental conditions in these peatlands may lead to altered microbial community structures and associated functions which may have implications for broader ecosystem function changes in peatlands.

Environmental Sciences & Ecology↗

Biochemical inhibition of acid phosphatase activity in two mountain spruce forest soils

The product inhibition of the 4-Methylumbelliferyl phosphate (MUB-P) decay rate, a measure of potential acid phosphatase activity, has not been considered in most of the published kinetic studies. The aim of this study was to determine the type and strength of the product inhibition in order to better define reaction conditions at which the acid phosphatase activity assay produces unbiased results. The MUB-P decay rate was measured in the forest floor and topsoil organic horizons of two spruce forest catchments at different initial MUB-P and P-PO4 3- concentrations. Furthermore, the type and strength of the inhibition was analyzed by non-linear regression. We found that MUB-P decay was competitively inhibited by the P-PO4 3- but also by dissolved organic P. By using estimated kinetic parameters, we calculated an underestimation of potential acid phosphatase activity by up to ~20% at concentrations of added MUB-P as high as 300 µmol g-1 dry weight and an incubation time one hour due to background inorganic and organic P concentrations in range of units of µmol per gram of dry soil. We discuss approaches that can be used to minimize the underestimation and show that the previously defined recommendations might not be always sufficient to avoid the bias. Therefore, we recommend to analyze progress curves at a wide range of initial MUB-P concentrations using non-linear methods when the enzyme assay is optimized for a given soil. When changes in inorganic and/or organic P concentrations are expected, we further recommend measuring background inorganic and organic P concentrations.

59 BASIC BIOLOGICAL SCIENCES↗

Legacies of precipitation influence primary production in Panicum virgatum

Precipitation is a key driver of primary production worldwide, but primary production does not always track year-to-year variation in precipitation linearly. Instead, plant responses to changes in precipitation may exhibit time lags, or legacies of past precipitation. Legacies can be driven by multiple mechanisms, including persistent changes in plant physiological and morphological traits and changes to the physical environment, such as plant access to soil water. Here, we used three precipitation manipulation experiments in central Texas, USA to evaluate the magnitude, duration, and potential mechanisms driving precipitation legacies on aboveground primary production of the perennial C 4 grass, Panicum virgatum. Specifically, we performed a rainout shelter study, where eight genotypes grew under different precipitation regimes; a transplant study, where plants that had previously grown in a rainout shelter under different precipitation regimes were moved to a common environment; and a mesocosm study, where the effect of swapping precipitation regime was examined with a single genotype. Across these experiments, plants previously grown under wet conditions generally performed better than expected when exposed to drought. Panicum virgatum exhibited stronger productivity legacies of past wet years on current-year responses to drought than of past dry years on current-year responses to wet conditions. Additionally, previous year tiller counts, a proxy for meristem availability, were important in determining legacy effects on aboveground production. As climate changes and precipitation extremes—both dry and wet—become more common, these results suggest that populations of P. virgatum may become less resilient.

54 ENVIRONMENTAL SCIENCES↗

Water-Weakening and Time-Dependent Deformation of Organic-Rich Chalks

Abstract The Ghareb Formation is a shallowly buried porous chalk in southern Israel that is being considered as a host rock for a geologic nuclear waste repository. Setup and operation of a repository will induce significant mechanical, hydrological and chemical perturbations in the Ghareb. Developing a secure repository requires careful characterization of the rock behavior to different loads. To characterize hydromechanical behavior of the Ghareb, several short- and long-term deformation experiments were conducted. Hydrostatic loading tests were conducted both dry and water-saturated, using different setups to measure elastic properties, time-dependent behavior, and permeability. A set of triaxial tests were conducted to measure the elastic properties and rock strength under differential loading at dry and water-saturated conditions. The hydrostatic tests showed the Ghareb began to deform inelastically around 12–15 MPa, a relatively low effective pressure. Long-term permeability measurements demonstrated that permeability declined with increasing effective pressure and was permanently reduced by ~ 1 order of magnitude after unloading pressure. Triaxial tests showed that water saturation significantly degrades the rock properties of the Ghareb, indicating water-weakening is a significant risk during repository operation. Time-dependent deformation is observed during hold periods of both the hydrostatic and triaxial tests, with deformation being primarily visco-plastic. The rate of deformation and permeability loss is strongly controlled by the effective pressure as well. Additionally, during holds of both hydrostatic and triaxial tests, it is observed that when water-saturated, radial strain surpassed axial strain when above effective pressures of 13–20 MPa. Thus, deformation anisotropy may occur in situ during operations even if the stress conditions are hydrostatic when above this pressure range.

58 GEOSCIENCES↗

Effects of moisture and aging upon decomposition of methyl iodide by reduced silver mordenite

Abstract Reduced silver mordenite has been considered as a sorbent for the capture of organic iodides, especially methyl iodide, from off-gases produced by aqueous used nuclear fuel reprocessing operations. The adsorption capacity of this material has been unpredictable especially when NO x and water are present. Previous work has found that a catalytic decomposition reaction is occurring on the surface but few determinations have been made of the kinetics of this reaction. The work presented tested the adsorption behavior and apparent catalytic reaction rate in humid conditions and compared those to dry conditions testing. Both experiments observed a first order reaction with rate constants of 0.0847 L/g sorbent/s and 0.1202 L/g sorbent/s respectively. Such a reduction in apparent rate constant is possibly due to either water obstructing methyl iodide adsorption or product desorption limitation. Changes in the adsorption profile were also apparent between these two, with the humid conditions experiment reaching saturation sooner than the dry conditions experiment. Additionally, an experiment into the effects of sorbent storage in a controlled laboratory environment was performed. The performance of the sorbent materials that were stored with silver in the zerovalent state was slightly inferior to those materials that were stored in ionic form (Ag + ) and reduced to zerovalent silver immediately prior to subjecting them to sorption test. The materials stored with silver in the ionic form (and reduced just prior to application) behaved essentially similarly to the freshly synthesized (and reduced) sorbents in the sorption tests. This suggests that zerovalent silver experiences some oxidation resulting in deactivation of some sites.

Goettsche, Heinrik↗

Exploiting chitosan to improve the interface of nanocellulose reinforced polymer composites

Cellulose nanofibrils (CNFs) have been widely used as a nanofiller for polymer composite reinforcement due to their excellent mechanical properties. However, CNF is produced in water and needs to be dried prior to use in composite materials. The presence of hydroxyl groups on the surface of CNF creates strong hydrogen bonding that makes it difficult and costly to dry. Additionally, the hydrophilicity at the fiber surface results in agglomeration of CNFs within many polymer matrices. In this study, chitosan (CS) was co-precipitated with CNF to produce a dual-bonding filler for use in poly (lactic acid) (PLA) composites. CS promotes improved interfacial interaction within the polymer matrix by forming strong hydrogen bonds with the CNF and potential covalent bonds with the PLA. Finally, the results confirmed that the addition of a small amount of CS significantly improved the mechanical properties compared to PLA + CNF composites and neat PLA. The detailed study of the PLA + CNF/CS composites reveals the synergetic effect of the hydrogen and covalent bonding mechanism for PLA reinforcement.

59 BASIC BIOLOGICAL SCIENCES↗

Chemomechanical weakening of muscovite quantified with in situ liquid nanoindentation

Abstract Chemomechanical weakening of layered phyllosilicate muscovite mica was studied as a function of chemical environment via in situ liquid-nanoindentation under four conditions (dry, deionized water, and two NaCl solutions of different pH). While traditional indentation analyses of layered materials with extreme mechanical anisotropy have been limited due to displacement bursts (pop-ins), here the bursts were used as proxies for delamination, fracture, and spalling events. Since displacement bursts during an indent represent a stochastic process, 120 indents were conducted for each condition to generate statistically significant amounts of data. In total, over 9000 bursts were assessed using a load–displacement threshold criterion, classifying this as a high-throughput nanoscale fracture technique. For each burst, initiation load, initiation displacement, plastic zone volume at initiation, and energy dissipation were analyzed. A power-law relationship between the burst load and burst energy was noted which separated the bursts into two continuous distributions: (1) bursts due only to the mechanics of the indent and (2) bursts due to both the mechanics of the indent and the environment. By using a cumulative probability distribution, it was found that the NaCl solutions decreased the minimum plastic zone volume necessary to initiate a displacement burst by an order of magnitude relative to the dry condition. Finally, the underlying mechanisms explaining the trends in initiation volume as a function of environment were discussed, with a focus on the chemomechanical degradation processes via chemical attack and cation exchange.

36 MATERIALS SCIENCE↗

Oxidation Behavior of Heat-Resistant Type $\mathrm{HK}$ Steel ($\mathrm{HK30Nb}$) at 800 °C

We report the cyclic oxidation behavior of HK30Nb heat-resistant steel processed by laser powder bed fusion (LPBF) was compared to its cast counterpart during exposures in air and air + 10% H 2 O at 800 °C. The specific finer microstructure and lower Mn of the LPBF alloy resulted in lower oxidation rates in dry air and faster establishment of a continuous Cr 2 O 3 scale in air + 10% H 2 O compared to coarse-grained cast HK30Nb with higher Mn. Differences in alloy mechanical strength and therefore their ability to accommodate high temperature and oxidation-induced stresses as well as differences in thermal expansion coefficients between the alloy and the formed oxides (Cr 2 O 3 only for the LPBF and Cr 2 O 3 and MnCr 2 O 4 for the cast specimens) during temperature cycling were found to result in a greater extent of spallation for the LPBF than for the cast alloy in dry air at 800 °C.

36 MATERIALS SCIENCE↗

CO2-Utilization Facilitated by Solid Reaction Mediums—A Review

Abstract This short review examines solid reaction mediums—specifically oxygen, CO 2 , and carbon carriers—within the framework of Chemical Looping (CL) to illuminate various CO 2 utilization pathways. The thermodynamic consideration for carrier selection is first discussed. This is followed by a summary of the key carrier types investigated to date, with an emphasis on elucidating the roles of compositional, structural, and surface properties of the various carriers toward their reactive performances. Besides assessing the performances of various oxygen carriers, their long-term performance, potential deactivation mechanism in the presence of CO 2, and strategies for their reactivation are also discussed in the context of chemical looping dry reforming of methane (CLDRM). While relatively underexplored, the current status of development, advantages, and potential limitations of CO 2 carriers in sorbent looping dry reforming of methane (SLDRM) and carbon carriers in chemical looping methane cracking (CLMC) are also reviewed and discussed. Emerging topics such as combined carriers are also covered along with a perspective for future research directions. Overall, this review aims to offer insights into the sustainable use of CO 2 through chemical looping, emphasizing the potential of solid reaction mediums across different carriers and the challenges associated with these solid reaction mediums.

Iftikhar, Sherafghan↗

Root lateral interactions drive water uptake patterns under water limitation

The plasticity of root water uptake determines the maintenance of transpiration during periods of water limitation and drought. However, the mechanistic basis of plant water uptake, as well as the implications of water uptake strategies at the individual and ecosystem scale remain elusive. We model three-dimensional root water uptake under variably saturated conditions for a one-hectare temperate forest plot for a growing season with a pronounced mid-season dry period. Variations in root architecture, hydraulic properties, and degree of lateral interaction between root systems produce divergent local responses to water limitation and provide insights on individual and community response to meteorological conditions. Results demonstrate the plasticity of ecosystem-scale responses to surface drying, where interacting roots shift regions of active uptake to deeper soil layers with less abundant root biomass. These shifts, a product of both root system and soil hydraulic properties, illustrate intimate links between root and soil hydraulics in determining plant water sourcing. Furthermore, we demonstrate that root lateral interactions are beneficial at the ecosystem-scale, even when trees compete for water. Specifically, a more spatially extensive root system facilitates access to a larger soil water reservoir, often ameliorating water limitation and reducing sharp water potential gradients. While the reduction of water stress is a benefit, it can be offset by increased root construction and maintenance costs associated with the larger rooting system. A plausible “viability” region of root communal co-existence is therefore implied where competitive pressures and root production costs are balanced by a potential water benefit.

54 ENVIRONMENTAL SCIENCES↗

Hydrometeorological sensitivities of net ecosystem carbon dioxide and methane exchange of an Amazonian palm swamp peatland

Here, we report ecosystem-scale CO 2 and CH 4 flux observations for an Amazonian palm swamp peatland over a two-year period in relation to hydrometeorological forcings. Seasonal and short-term variations in hydrometeorological forcing had a strong effect on carbon dioxide and methane fluxes. High air temperature and vapor pressure deficit exerted an important limitation on photosynthesis during the dry season, while latent heat flux appeared to be insensitive to these climate drivers. Evidence from light-response analyses and flux partitioning support that photosynthetic activity was downregulated during dry conditions, while ecosystem respiration was either inhibited or enhanced depending on water table position. The cumulative net ecosystem carbon dioxide exchange indicated that the peatland was a significant carbon dioxide sink ranging from –465 (–279 to –651) g C m -2 y -1 in 2018 to –462 (–277 to –647) g C m -2 y -1 in 2019. The forest was a methane source of 22 (20 to 24) g C m -2 y -1 , similar in magnitude to other tropical peatlands and larger than boreal and arctic peatlands. Furthermore, the annual carbon budget of this Amazonian palm swamp peatland appears to be a major carbon sink under current hydrometeorological conditions, but evidence indicates that the sink strength is vulnerable to future climate change.

54 ENVIRONMENTAL SCIENCES↗

Turbulence regimes in the nocturnal roughness sublayer: Interaction with deep convection and tree mortality in the Amazon

We investigated the influence of seasonality and proximity to the forest canopy on nocturnal turbulence regimes in the roughness sublayer of a Central Amazon forest. Since convective systems of different scales are common in this region, we also analyzed the effect of extreme wind gusts (propagated from convective downdrafts) on the organization of the turbulence regimes, and their potential to cause the mortality of canopy trees. Our data include high-frequency winds, temperature and ozone concentration at different heights during the dry and wet seasons of 2014. In addition, we used critical wind-speed data derived from a tree-winching experiment and a modeling study conducted in the same study site. Two different turbulence regimes were identified at three heights above the canopy: a weakly stable (WS) and a very stable regime (VS). The threshold wind speeds that mark the transition between turbulence regimes were larger during the dry season and increased as a function of the height above the canopy. The turbulent fluxes of sensible heat and momentum during the WS accounted for 88% of the entire nighttime flux. Downdrafts occurred only in the WS and favored a fully coupled state of wind flow along the canopy profile. The destructive potential of winds was four times higher than on nights without downdrafts.

54 ENVIRONMENTAL SCIENCES↗