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At least 559 records · Page 31

BSEC Air Quality: Stationary Aerosol Composition and Mass Concentration at Baltimore

Data is 10-min average mass composition and mass concentration from the TOF-ACSM-X and Aethalometer AE33. TOF-ACSM-X reports fine (less than 2.5 um diameter) non-refractory aerosol, including organic aerosol, sulfate, nitrate, ammonium, and non-refractory chloride. Aethalometer measured the attenuation at different wavelengths for aerosol collected onto tape; one wavelength is used to convert to black carbon mass concentration. Also reported is the elemental ratios determined for organic aerosol (O/C, H/C, and organic matter to organic carbon ratio, OM/OC).

aerosol↗

Sulfonamide and Sulfonamido-phenol Ligands for Extraction of f-Elements from Alkaline High-Level Waste

Alkaline High Level Waste (HLW) has been accumulated at Hanford and Savannah River Sites as a result of reprocessing for nuclear weapons production during the cold war. A large volume (∼100 MGal) has been accumulated in carbon steel tanks at Savannah River (SRS) and Hanford. The tank waste contains three separate phases generated when NaOH was added to previously acidic Purex raffinates: 1-2 Supernatant liquid, salt-cake, and sludge. The sludge consists mainly of insoluble hydroxides of transition metals while the supernate and salt-cake contain caustic-soluble materials, including salts of highly radioactive fission products Cs(I) and Sr(II). Current treatment of alkaline HLW in SRS includes: i) The Actinide Removal Process (ARP), which is based on sorption of {sup 90}Sr and Actinides (An) on monosodium titanate (MST), also known as 'alpha-strike' process, followed by ii) Caustic Side Solvent Extraction (CSSX),4 which is used for the extraction of {sup 137}Cs by modified calixarenes in a hydrocarbon diluent. Residual actinides in some tanks are removed after CSSX by an additional ARP process commonly referred to as 'alpha-finishing'. Despite the success of ARP for Sr and An removal, as it is a sorption process, it represents the kinetic bottleneck of integrated salt waste processing. Hence potential introduction of additional organic ligands for actinide extraction (in a modified CSSX process) could simplify the overall integrated process, making it more efficient and economical, with less titanate needed and shorter sorption time, as some of the actinide component would be removed during CSSX. In this study tri-sulfonamide and o-sulfonamido-phenol (mono-sulfonamide) ligands have been studied as extractants for Sm(III), which is being used as an Am(III) surrogate. Our prior studies in the group using a tri-sulfonamide (iPr-tsa-B) showed favorable extraction for Sm(III) nitrate salts from alkaline solutions. Mono-sulfonamides possess similar orientation of binding sites to pyrocatechols, which have been found to be good ligands for Am(III) binding and extraction from alkaline media. Tri-sulfonamide of the type iPr-tsa-B6 (1 mM in CH{sub 2}Cl{sub 2} solution) was studied for Ln{sup 3+} extraction using Sm(NO{sub 3}){sub 3}.6H{sub 2}0 (10 and 25 μM) in alkaline solution of NaOH (0.05, 0.1, 0.2, 0.3 mM) / 0.1 M NaNO{sub 3}. Stripping of the organic phase was done using 0.1 M HNO{sub 3} and quantification of Sm{sup 3+} was done using ICP-OES at 359.3 nm. The need to improve stability of the complex led to synthesis of compounds with N-donor site closer to the central benzene ring to facilitate cation-π interactions. Synthesis of tri-sulfonamide type A: a) Chloromethyl methyl ether, SnCl{sub 4}, CH{sub 2}Cl{sub 2}, 0 deg. C, N{sub 2}, 4 h, 57%; b) NaN{sub 3}, reflux in H{sub 2}O/acetone for 22 h, 80%; c) PPh{sub 3}, THF/H{sub 2}O, 22 h, 79%; d) p-toluene sulfonyl chloride, Et{sub 3}N, 1,2-DCE, 22 h. Extraction: Sm(NO{sub 3}){sub 3}.6H{sub 2}O (2 mM) in 5 ml of aqueous NaOH (pH 10.5 - 14) + 6 ml of CH{sub 2}Cl{sub 2} solution of msa (20 mole equiv.) were rotated on a wheel (60 rpm; 20 h). Stripping: 5 ml of 0.1 M HNO{sub 3} + CH{sub 2}Cl{sub 2} solution of msa (after extraction, centrifugation and filtration) was rotated on the wheel (60 rpm; 20 h). Sm{sup 3+} was quantified using UV-Visible spectrophotometry.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Analysis of Using a Hybrid ZIRCEX Process to Generate High-Assay Low-Enriched Uranium (HALEU) - 20158

Idaho National Lab (INL) is investigating the feasibility of providing High-Assay Low Enriched Uranium (HALEU) by recovering Highly Enriched Uranium (HEU) from spent nuclear fuel (SNF) and downblending the HEU with natural, low-enriched, or depleted uranium (NU, LEU, or DU). That investigation identified that significant quantities of HALEU could be produced with a Hybrid ZIRCEX process to further advanced reactor research while reducing INL's environmental liability. Many new advanced reactor designs are being developed with improved safety, efficiency, and economics. Most require nuclear fuel with U-235 enrichment between 5% and 20%, which is defined as HALEU. Although technically feasible, there is no current domestic capability to make HALEU in the US. While it is anticipated that industry will provide HALEU through commercial enrichment once advanced reactors mature, until a market is established, an interim source of HALEU is needed to enable research and demonstration. An interim source of HALEU could be provided by recovering the HEU in some DOE-managed SNF and downblending it to between 5% and 20% using the Hybrid ZIRCEX Process. ZIRCEX is a dry head-end process to remove cladding (zirconium or aluminum) from SNF. Drying of the SNF is needed prior to introduction to ZIRCEX. After cladding removal, uranium and fission products in the bed material are oxidized and elutriated. In a Hybrid ZIRCEX process, the HEU process stream is sent to a very compact, modular solvent extraction process for uranium purification. The uranyl nitrate from solvent extraction is denitrated and calcined to produce a HALEU product ready for fuel fabrication. The long-lived fission products from solvent extraction are immobilized in glass using a small in-can melt. By removing the cladding before dissolution, the volume of glass waste is reduced by a factor of up to 300 times (when compared to not removing the cladding from the fuel). Other radioactive wastes from the process could be disposed of as Class A or Class B low-level waste. In addition to producing HALEU for advanced reactors, consumption of SNF would reduce DoE's environmental liability. Incorporating low-enriched spent fuel (versus exclusive use of LEU, DU, or NU) into the downblending scheme could reduce the SNF inventory even further. Several downblending and enrichment scenarios using INL fuels were investigated in this study. The results of this analysis show that the Hybrid ZIRCEX process could make a significant contribution to needed HALEU feedstock and reduce the environmental liability of managing SNF at INL. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Innovations in Sustainable Passive Wastewater Treatment - 20236

Sustainable water treatment systems, engineered to mimic natural processes and utilize natural materials, yield economic and environmental benefits through reductions in long term operational inputs, including: power, chemicals, and labor. Golder is an industry leader in the development and implementation of sustainable technologies at operating and closed mines. We continue to innovate these technologies and customize solutions to meet client needs by applying past experience and focused research. Sustainable (or passive) water treatment systems include ponds, wetlands, flow-through natural media beds, and limestone drains. These systems can blend in with a natural environment, are highly cost-effective for long-term water treatment, and can outcompete traditional active treatment technologies. Application of sustainable technologies relative to active technologies can be influenced by the influent water matrix, effluent limitations, flow rate of water requiring treatment, and available land area. In this presentation, four Golder-developed systems are reviewed as case studies, demonstrating our continued progressive approach to advancing sustainable water treatment technologies to meet industry needs. These case studies focus on design innovations and operational performance from data collected from the operational systems. Resources (power, chemicals, labor) required for the operation of each case study are compared with those that would be required for operation of their active treatment technology alternatives. - Case Study 1 presents an anaerobic biochemical reactor (BCR), a technology typically implemented for metals treatment and acid neutralization, for the treatment of sulfate to low concentrations (<250 mg/L). Active treatment via reverse osmosis (RO) membrane filtration is typically required for treatment of sulfate to similar concentrations, this innovation provides potential for sustainable treatment to replace the need for energy, chemical, labor, and waste (brine) intensive RO treatment for specific applications. Magnetite waste rock materials from the site were upcycled for use in this system to provide sequestration of the sulfide generated in the BCR. - Case Study 2 examines another novel application of the conventional BCR, modified for the removal of radionuclides and metals (uranium, radium, and selenium) at a closed uranium mine. - Case Study 3 presents implementation of sustainable treatment for mine drain water from a historic mine site, now a state park with around 100,000 visitors per year. The system includes a pond, wetland, and manganese removal bed surrounded by public trails designed to maintain the character of the park. The system treats for arsenic, iron, and manganese at relatively high flows (up to 1,200 gpm), with large seasonal fluctuations in flow and quality. - Case Study 4 is a unique project for which Golder is currently designing a sustainable treatment system, with no energy input, to treat nitrate in mine water post-closure at a site near the arctic circle. In this unprecedented application, climate, management of freshet, and space availability presented substantial technical challenges. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solubility Predictions for Hanford Tank Concentrates with HSC - 20459

The commercially available Outotec HSC 9.9.0{sup R} provides excellent predictions for the solubilities of many species for Hanford waste tank concentrates. The HSC solubility predictions with a Harvie activity model agreed well with five boildowns that showed solubility limits for NaNO{sub 3}, NaNO{sub 2}, Na{sub 2}CO{sub 3}, NaF, Na{sub 2}SO{sub 4}, and Na{sub 3}PO{sub 4}. However, the HSC did not predict density and therefore water content very well and therefore we used the measured densities and derived water content from the difference between measured density and assays. Furthermore, we adjusted the HSC enthalpy for the minor species Na{sub 3}PO{sub 4}*NaF double salt in order to fit the five boildowns as well. Previous work has shown that gibbsite becomes and remains supersaturated in all of these boildowns and so there was no alumina precipitation despite supersaturation. Furthermore, an equilibrium model like HSC always shows complete oxidation of any TOC in the presence of nitrate and nitrite. We therefore suppressed the HSC oxidation of acetate and oxalate in order to fit measured acetate and oxalate solubilities as TOC. Space in Hanford waste tanks is very limited and therefore evaporator campaigns continue to recover needed tank space from dilute tank liquids. Prior to each evaporator campaign, a boildown of a sample of tank liquid for each campaign provides a basis for planning by measuring density, water activity, soluble species, and solids precipitation as a function of concentration at 18 deg. C. These boildowns then provide validations and calibrations for the HSC solubility prediction for Hanford wastes. Previous work has shown the solubilities of minor electrolytes in these five boildowns follow rather simple power law solubility products. Hanford's 222-S laboratory has reported each of five boildowns for concentrated liquids from five waste tanks and tank blends. All boildowns eventually showed the precipitation of the dominant electrolyte, NaNO{sub 3}, and overall solution activity largely drives all solubility. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Defining a Metric to Assess Leachability of Contaminants from Cementitious Waste Forms in Lab Testing Related to Hanford - 20478

This paper reports on the determination of performance metrics for the release of four contaminants (technetium, iodine, nitrate, and chromium) from a theoretical supplemental low-activity waste (LAW) inventory of grout in the Hanford Integrated Disposal Facility (IDF). The performance metric was defined as a retardation factor, R, that can be used to quantify a waste form's ability to retain one contaminant compared with an un-retarded species (e.g., sodium). By setting the target R value at the magnitude required to maintain concentrations of the contaminants below the drinking water standard at the point of compliance for the IDF, a bar for grout leach performance can be established for screening laboratory leach test data. The R can be converted to a corresponding laboratory-observed diffusivity value against which to assess leach test data. The individual performance metrics were determined through an iterative set of simulations using a variable saturation and transport flow model of a grout waste form inventory in the IDF to calculate the resulting concentration-based requirements at the point of compliance. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

ASMS 2024 Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision Induced Dissociation

Investigation of Uranyl Perchlorate Anion Complexes in the Gas Phase via Infrared Multiphoton Dissociation and Collision Induced Dissociation Brittany D. M. Hodges, Christopher A. Zarzana, JungSoo Kim, Jonathan Martens, and W. C. M. Berden Introduction (120 words max) Effects of electronic structure on chemical bonding and reactivity play critical roles shaping the chemical bonding and reactivity behaviors of heavy elements. Understanding the role of f electrons in bond formation between the actinide-series elements like uranium with other ligands is critical for solving technical challenges associated with these heavy elements, important to nuclear fuel cycles, efficient separations of rare earth metals, and understanding the chemistry of stored nuclear fuels and related environmental management sites. In this study, we further examine the interactions between uranyl and the perchlorate ion in order to understand the structures of these ions through the use of IRMPD. Here we report the IRMPD spectra of [UO2(ClO4)3]-, [UO3(ClO4)2]-, and a proposed transition state. Methods (120 word max) IRMPD spectra and CID spectra were acquired using a Bruker amaZon QIT/MS instrument at the Free-Electron Lasers for Infrared eXperiments (FELIX) laboratory at Radboud University. The FELIX QIT/MS is modified to allow for the high-intensity tunable IR beam from FELIX to be directed into the ion packet, resulting in multiphoton dissociation that is measured only when the IR frequency is in resonance with an adequately high absorption vibrational mode of the mass-selected complex. DFT geometry optimizations and frequency calculations using the Gaussian suite of programs were performed using B3LYP, TPSSh, and PBE0 level of theory with 6-31+G(d) basis for the O, C, H, and N atoms and the SDD basis set for U. The SDD basis set employs the Stuttgart/Dresden effective core potential. Preliminary Data or Plenary Speakers Abstract (300 words max) Metal ion clusters of uranyl perchlorate were formed via direct electrospray ionization. For each metal ligand complex of interest, the parent ion was isolated and collision induced dissociation fragmentation and Infrared Multiphoton Dissociation (IRMPD) fragmentation spectra were acquired. Results presented here are the first look at the IRMPD spectra of [UO3(ClO4)2]-, [UO2(ClO4)3]-. Structures were examined using Gaussian at different levels of theory B3LYP level of theory, TPPSh and PBE0 levels, to reflect the behaviors of uranium metal ligand complexes most accurately. In these structures, we identified an overlap between each of these uranyl stretches resulting in their largely being obscured by a perchlorate mode. The CID product spectra agree with similar structures reported by Groenewold for uranyl nitrate in 2006 (10.1021/ja058106n).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Condition-dependent NO x adsorption/desorption over Pd/BEA: A combined microreactor and in situ DRIFTS study

Pd/BEA is chosen as a model passive NO x adsorber (PNA) to elucidate the effect of the feed gas composition on the NO x adsorption/desorption behavior. The Brønsted acid and the partially hydrolyzed framework Al (P-HAl(OH)) sites in HBEA adsorb NO and NO 2 under dry conditions. Moreover, the performance of HBEA is not affected by CO, while CO inhibits nitrate formation and promotes NO adsorption via the Pd(NO)(CO) complexes formation over Pd/BEA. H 2 O inhibits NO adsorption over the Brønsted acid and P-HAl(OH) sites, and ionic Pd is the only active site for NO x adsorption under wet conditions. Furthermore, NO adsorption over hydrated Pd (Pd 2+ (OH)(NO)(H 2 O) 3 ) is weaker than NO adsorption over bare ionic Pd (Z 2 [Pd 2+ (NO)], Z[Pd 2+ (OH)(NO)]). Dehydration of Pd 2+ (OH)(NO)(H 2 O) 3 forms more stable Z[Pd 2+ (OH)(NO)] during desorption. Here, the NO adsorption capacity of Pd/BEA improves in the presence of CO under both dry and wet conditions by forming a stable carbonyl–nitrosyl complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A Crosslinked Ionic Organic Framework for Efficient Iodine and Iodide Remediation in Water

Abstract Iodine is widely used as an antimicrobial reagent for water disinfection in the wilderness and outer space, but residual iodine and iodide need to be removed for health reasons. Currently, it is challenging to remove low concentrations of iodine and iodide in water (≈5 ppm). Furthermore, the remediation of iodine and iodide across a broad temperature range (up to 90 °C) has not previously been investigated. In this work, we report a nitrate dimer‐directed synthesis of a single‐crystalline ionic hydrogen‐bonded crosslinked organic framework (H C OF‐7). H C OF‐7 removes iodine and iodide species in water efficiently through halogen bonding and anion exchange, reducing the total iodine concentration to 0.22 ppm at room temperature. Packed H C OF‐7 columns were employed for iodine/iodide breakthrough experiments between 23 and 90 °C, and large breakthrough volumes were recorded (≥18.3 L g −1 ). The high iodine/iodide removal benchmarks recorded under practical conditions make H C OF‐7 a promising adsorbent for water treatment.

Zhang, Mingshi↗

Impact of landscape design on the greenhouse gas emissions of shrub willow bioenergy buffers in a US Midwest corn-production landscape

Previous studies have evaluated the economics and ecosystem services of perennial bioenergy crops when replacing grain crops on marginal (environmentally critical and/or underproductive) lands. This study used life-cycle analysis (LCA) to investigate the greenhouse gas (GHG) emissions of perennial crops when grown in targeted landscape positions and their impact in reducing nitrogen leaching. Specifically, LCA was performed to evaluate the GHG emissions of growing shrub willow on marginal lands in the Indian Creek watershed in Illinois to assess the sustainability of strategically planted willow buffer strips. Willow was grown as a short-rotation woody crop with a 21-year rotation under three scenarios including a business-as-usual (BAU) field-scale production with nitrogen fertilizer application and two unfertilized subfield buffer scenarios – landscape single subfield (LSSF) or landscape multiple subfields (LMSF) – grown alongside cornfields to reduce nitrate leaching. Each scenario also considers three field sizes, 2.0, 10.1, and 40.5 ha. The average annual GHG emissions from willow production and depot transportation were 0.32–0.77 Mg-CO 2 e ha-1 with the lowest emissions for the LSSF scenario and highest for the BAU. The GHG emissions for the LSSF and BAU scenarios are independent of field size, whereas LMSF emissions increase with increasing field size, 0.41 Mg-CO 2 e ha-1 at 2.0 ha and 0.76 Mg-CO 2 e ha-1 at 40.5 ha. Emission results were most sensitive to the willow yield, followed by fertilizer application rate (BAU only), harvest fuel consumption, and transportation distance.

09 BIOMASS FUELS↗

Cellular Phosphate Sensing and Anion Binding by an Azacrown‐Calixpyrrole Hybrid

A hybrid receptor-sensor for anions originating from the merging of positively charged ammonium moieties for electrostatic attraction/stronger binding of azacrowns with directionality of calixpyrrole hydrogen bond donors for selectivity is investigated. As demonstrated this hybrid receptor-sensor shows a remarkable selectivity for orthophosphate even in the presence of other phosphates and anions found in cellular materials (K assoc H 2 PO 4 − >H 2 P 2 O 7 2− >AMP − ≫ADP 2− or ATP 3− over halides, nitrate, or hydrogen sulfate; all Na + salts in water) but also cellular polyphosphate or phospholipids. This selectivity is harnessed in a real-time monitoring of cell lysis by lysozyme, which releases orthophosphate and other phosphates and anions from the cells. This sensitive (LOD 0.4 μM) fluorescence-based microscale method compares favorably with the state-of-the-art techniques but can easily be practiced in a high-throughput screening (HTS) manner. The anion binding and selectivity in aqueous solutions were investigated by NMR and put in context with phosphate binding of the parent calix[4]pyrrole. The microscopic understanding of anion binding by the hybrid receptor was then obtained from a combination of density functional theory (DFT), classical molecular dynamics (MD) with explicit water solvation, and ab initio MD (AIMD) simulations. Correlating the NMR and fluorescence binding data with studies of solvation of the receptor, phosphate anion, and the resulting complex confirms the binding is largely driven by entropic component (TΔS) associated with receptor and anion desolvation.

Anions↗

Pyrrole‐Imine Macrocycle: Self‐Organizing Cross‐Reactive Anion Receptor and Sensor

Self-organizing macrocyclic receptor-sensors for phosphorus oxyanions, phosphates, and phosphonates comprising imine moieties were prepared by condensation of dipyrrolylmethane dicarbaldehyde with diethylene triamine. The incorporation of flexible ethylene moieties endows the macrocycle with unprecedented flexibility and ability to accommodate numerous phosphorus oxyanions from orthophosphate to large anions such as ATP or phosphonate glyphosate. The anion binding was elucidated by NMR titrations, low-temperature NMR, and NOESY NMR. The incorporation of dansyl fluorophore enables sensing of anions using the fluorescence signal, whereas the changes in fluorescence intensity, width of the fluorescence band, and position of the maxima are analyte-specific and useful in recognition and identification of eleven different P-oxyanions in water. The affinity (K assoc ) for Na + salts was H 2 PO 4 − ≈ Methylphosphonate > H 2 P 2 O 7 2− > Phenylphosphonate- > Glyphosate 2− > AMP 2− > ADP 2− > ATP 2− . Interestingly, phosphonates, including methylphosphonate and glyphosate anions, were also found to display a strong affinity (K assoc ∼10 6 M −1 ) while halides, nitrate, carbonates, or hydrogen sulfate did not show a significant affinity. The determined fluorescence spectral parameters were used to classify the 12 analytes (11 anions and water) using Linear Discriminant Analysis (LDA). Quantification was performed using LDA and Support Vector Machine (SVM), and the phosphonate concentrations in unknown samples were determined with an error of 3.5% or lower.

anions↗

Thorium Bis‐Salophen Trimers as Anion Detectors and Binding Agents

Bis‐salophen ligands are the condensation product of a tetramine and a salicylaldehyde derivative. They feature two binding sites, both of which are tetradentate with mixed O/N donor atoms. Reaction with the ligand precursor and thorium nitrate tetrahydrate forms a 3:3 metal‐to‐ligand trimer with a ΔΔΔ‐chirality confirmed by X‐ray crystallography of a racemic single crystal. The structure has a pore in the center of the triangular structure measuring 6.22 Å at its narrowest point. This compound is air‐ and water‐stable as well as soluble in organic solvents. Here, this compound was screened with a series of tetrabutyl ammonium halide salts, and tetrabutylammonium (TBA) chloride showed the strongest binding to the complex. After the addition of 2 equivalents of TBACl, the complex and salt precipitate out of solution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electrocatalytic CN Coupling: Advances in Urea Synthesis and Opportunities for Alternative Products

Urea is an essential fertilizer produced through the industrial synthesis of ammonia (NH 3 ) via the Haber–Bosch process, which contributes ≈1.2% of global annual CO 2 emissions. Electrocatalytic urea synthesis under ambient conditions via CN coupling from CO 2 and nitrogen species such as nitrate (NO 3 − ), nitrite (NO 2 − ), nitric oxide (NO), and nitrogen gas (N 2 ) has gained interest as a more sustainable route. However, challenges remain due to the unclear reaction pathways for urea formation, competing reactions, and the complexity of the resulting product matrix. This review highlights recent advances in catalyst design, urea quantification, and intermediate identification in the CN coupling reaction for electrocatalytic urea synthesis. Furthermore, this review explores future prospects for industrial CN coupling, considering potential nitrogen and carbon sources and examining alternative CN coupling products, such as amides and amines.

Chemistry↗

Proton nuclear magnetic resonance (1H NMR) of flammable organic chemicals in radioactive high–level supernatant waste at the Savannah River Site (SRS)

The Savannah River Site stores approximately 36 million gallons of radioactive and hazardous waste that contains approximately 245 million curies. The waste is sent through various chemical processes to reduce its volume and to separate various components. The facility plans to replace formic acid (a chemical used to reduce soluble mercury) with glycolic acid. Recycle solution with glycolate may flow back to the tank farm, where the glycolate can generate hydrogen gas by thermal and radiolytic mechanisms. The current analytical method for detecting glycolate (ion chromatography) in supernatant requires a large dilution to reduce interference from the nitrate anions. Hydrogen nuclear magnetic resonance is an analytical method that requires less sample dilution. It takes advantage of the CH 2 group in glycolate. Liquid samples were spiked with four different levels of glycolate to build a calibration line, as it is recommended in the standard addition method. The detection and quantitation limits determined were 1 and 5 ppm, respectively, for 32 scans, which is well below the process limit of 10 ppm. In one test, 800 scans of a supernatant spiked with 1 ppm glycolate resulted in a -CH 2 peak with a signal-to-noise ratio of 36.

1H↗

Effects of Livestock Exclusion on Stream Habitat and Aquatic Biota: A Review and Recommendations for Implementation and Monitoring

Abstract To inform riparian restoration, research, and monitoring and to provide management recommendations, we reviewed published studies evaluating the physical and biological effectiveness of livestock exclusion and grazing reduction on various metrics in riparian and aquatic areas. We identified 95 North American studies that reported the effects of livestock grazing reduction on physical habitat (channel morphology, mesohabitats, substrate, and bank stability), biological assemblages (riparian vegetation, macroinvertebrates, fish, and birds), and water quality metrics (temperature, nitrates, phosphorus, and turbidity). Most studies reported that methods to reduce or exclude livestock decreased channel width, width-to-depth ratio, bank erosion, soil bulk density, bare ground, water temperature, nitrogen, and phosphorus and increased riparian vegetation (cover, height, productivity, biomass, and abundance), riparian bird abundance, and young-of-the-year fishes. Results for channel depth, instream substrate, mesohabitats, water depth, juvenile and adult fishes, and macroinvertebrates showed no consistent response to exclusion. Project success was influenced by the time since exclusion; whether there was complete exclusion or continued grazing; and local climate, geology, and soils. Apart from bank erosion and stability, most of the physical and biological metrics took more than a decade to respond to livestock exclusion. However, coupling exclusion with planting and other restoration measures decreased the recovery time. Complete exclusion of livestock produced more consistent improvements in riparian condition and other metrics than rest–rotation or other grazing management strategies. Understanding how physical and biological metrics respond to livestock exclusion will require (1) focused, long-term studies using before–after or before–after, control–impact designs; and (2) monitoring of metrics that most consistently respond to exclusion. Ultimately, the design of exclusions should be driven by local climate, geology, biophysical conditions, and management history. Our results highlight the need for watershed-scale approaches to excluding livestock from broad areas and the need for implementation monitoring to ensure that fencing and other exclusion measures continue to exclude livestock and produce the desired responses.

Krall, Michelle↗

Nitrogen Status Rewires Transcriptional Regulation of Dhurrin, a Dual‐Purpose Defense Metabolite in Sorghum bicolor

Dhurrin, a cyanogenic glucoside, plays an important role in Sorghum bicolor physiology and defense. The concentration of dhurrin in sorghum is influenced by both nitrogen status and stage of plant organ development. While nitrogen resupply activates the expression of genes for dhurrin biosynthesis, the molecular mechanisms underlying this regulation remain unclear. In this study, we investigated the transcriptional response of sorghum to nitrogen resupply following growth under nitrogen-limiting conditions. Using a time-course design, we measured hydrogen cyanide potential (HCNp), growth, and nitrate content at 0-, 2-, 6-, 12-, 24-, 36-, 48-, and 60-h after resupply and collected tissue for RNAseq analysis in parallel for analysis of gene expression and construction of gene regulatory networks (GRNs). HCNp (mg g −1 DW) increased significantly in leaf and stem tissues following nitrogen resupply, with increases in the leaf partially driven by continued declines in controls under ongoing nitrogen stress. Expression of the dhurrin pathway genes was upregulated in leaves from 24 h after nitrogen resupply, with diel expression patterns observable over the remaining time points. No upregulation was observed in roots or stems, suggesting that developmental context overrides environmental cues. GRN analysis identified candidate transcription factors regulating dhurrin biosynthesis genes, including members of the MYB, bZIP, and GARP-type transcription factor families. Some of these candidate transcription factors may be involved in relieving senescence-associated suppression of dhurrin biosynthesis and link nitrogen signaling to pathway activation. These findings provide new insight into the nitrogen-responsive regulation of dhurrin in sorghum, highlighting candidate regulators for future functional characterization.

S. bicolor↗