Search for: All records

Nature-based treatment technologies such as denitrifying woodchip bioreactors (WBRs) are employed to manage nitrogen (N) pollution from agricultural nonpoint sources. Due to variability in environmental conditions like temperature and discharge, it is challenging to achieve consistent treatment effectiveness with these passive systems. To improve nitrate (NO3–) load reductions in a field-scale WBR in New York State during cool spring weather, we designed a system for controlled exogenous carbon (C) dosing, allowing rates of C dosing to respond in real time to changing discharge and NO3– concentrations. Treatment efficiencies for NO3–, acetate mass balances, and other bioreactor properties were monitored from April 5 to June 10, 2023. Biostimulation with 7.5 mg C/L acetate (assuming complete mixing of injected acetate with bioreactor pore water) increased NO3– removal rates up to 5-fold compared to a model-based scenario of baseline bioreactor performance, and were as high as 0.4 mg NO3––N L–1 h–1 while water temperatures were <12 °C. Increasing acetate concentrations beyond 7.5 mg C/L did not confer a clear improvement in NO3– removal rates. Cumulative N load reductions increased from 11.3% under the baseline scenario without C dosing to 24.1% with C dosing. The mass ratio of metabolized C to additional N removal was 2.5:1, although the total dosed C/N mass ratio was 5.1:1 due to incomplete acetate utilization in the reactor. We found evidence that C dosing could enhance the future release of dissolved organic N (DON) and dissolved organic C related to biofilm sloughing. The expense of acetate, with a cost efficiency of 86 USD/kg N, was the main cost driver of the real-time control approach. Our results demonstrate the potential of real-time control of C dosing to meaningfully improve nonpoint source N removal during cool spring conditions but also highlight opportunities for methods to improve acetate utilization efficiencies in order to improve the overall cost-effectiveness of the approach. 

Abstract We investigate solvent effects in the hydrodeoxygenation of 4-propylguaiacol (4PG, 166 amu), a key lignin-derived monomer, over Ru/C catalyst by combinedoperandosynchrotron photoelectron photoion coincidence (PEPICO) spectroscopy and molecular dynamics simulations. With and without isooctane co-feeding, ring-hydrogenated 2-methoxy-4-propylcyclohexanol (172 amu) is the first product, due to the favorable flat adsorption configuration of 4PG on the catalyst surface. In contrast, tetrahydrofuran (THF)—a polar aprotic solvent that is representative of those used for lignin solubilization and upgrading—strongly coordinates to the catalyst surface at the oxygen atom. This induces a local steric hindrance, blocking the flat adsorption of 4PG more effectively, as it needs more Ru sites than the tilted adsorption configuration revealed by molecular dynamics simulations. Therefore, THF suppresses benzene ring hydrogenation, favoring a demethoxylation route that yields 4-propylphenol (136 amu), followed by dehydroxylation to propylbenzene (120 amu). Solvent selection may provide new avenues for controlling catalytic selectivity. 

This paper proposes a computer vision-based workflow that analyses Google 360-degree street views to understand the quality of urban spaces regarding vegetation coverage and accessibility of urban amenities such as benches. Image segmentation methods were utilized to produce an annotated image with the amount of vegetation, sky and street coloration. Two deep learning models were used -- Monodepth2 for depth detection and YoloV5 for object detection -- to create a 360-degree diagram of vegetation and benches at a given location. The automated workflow allows non-expert users like planners, designers, and communities to analyze and evaluate urban environments with Google Street Views. The workflow consists of three components: (1) user interface for location selection; (2) vegetation analysis, bench detection and depth estimation; and (3) visualization of vegetation coverage and amenities. The analysis and visualization could inform better urban design outcomes. 

Abstract Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal–organic frameworks, pre‐organized multi‐ion “secondary building units” (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi‐step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small‐angle X‐ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q 3 8 polyanions formed through cross‐linking and polymerization of smaller silicate monomers and other oligomers. These Q 3 8 are stabilized by hydrogen bonds with surrounding H 2 O and tetramethylammonium ions (TMA + ). When Q 3 8 levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA) x (Q 3 8 )⋅ n  H 2 O] ( x −8) clathrate complexes into step edges on the crystals. 

Hierarchical nucleation pathways are ubiquitous in the synthesis of minerals and materials. In the case of zeolites and metal–organic frameworks, pre-organized multi-ion “secondary building units” (SBUs) have been proposed as fundamental building blocks. However, detailing the progress of multi-step reaction mechanisms from monomeric species to stable crystals and defining the structures of the SBUs remains an unmet challenge. Combining in situ nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy, we show that crystallization of the framework silicate, cyclosilicate hydrate, occurs through an assembly of cubic octameric Q38 polyanions formed through cross-linking and polymerization of smaller silicate monomers and other oligomers. These Q38 are stabilized by hydrogen bonds with surrounding H2O and tetramethylammonium ions (TMA+). When Q38 levels reach a threshold of ≈32 % of the total silicate species, nucleation occurs. Further growth proceeds through the incorporation of [(TMA)x(Q38)⋅n H2O](x−8) clathrate complexes into step edges on the crystals.