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At least 631 records · Page 35

Hygroscopic Metal-Complex Coated Metal Foam for Moisture Management

Moisture management for improving indoor air quality is critical for health and thermal comfort. Recently, the use of desiccant-coated heat exchangers (HXs) has emerged as a promising dehumidification approach to reduce energy consumption as compared with conventional vapor compression-based air dehumidification. The desiccant material is a key component of dehumidification performance. However, currently used desiccant materials have a low moisture uptake capability and require a high temperature for regeneration. The current study investigated the dehumidification performance of a metal-complex-based hygroscopic desiccant-coated metal foam HX. Furthermore, the results revealed that the desiccant-coated foams display increased hydrophilicity compared with the uncoated metal surfaces. Additionally, the desiccant coating had superior moisture absorption capability of more than 2 g/g desiccant , which is much higher than commonly used zeolite and silica gels. Wind tunnel experiments showed that the coating absorbs moisture from humid air and can be effectively regenerated at low temperatures. Additionally, the coating did not increase the pressure drop of the HX. Overall, the results of this study suggest that this desiccant-coated metal form can potentially be used for moisture management in the building sector.

Atmospheric chemistry↗

Centimeter-Scale Pillared-Layer Metal–Organic Framework Thin Films Mediated by Hydroxy Double Salt Intermediates for CO 2 Sensor Applications

Fabrication of metal–organic framework (MOF) thin films over macroscopic surface areas is a subject of great interest for gas sensor application platforms such as optics and microelectronics. However, a direct synthesis of MOF films at ambient conditions, in particular pillared-layer MOF films due to their anisotropic structures, remains a significant challenge. Herein, we demonstrate for the first time a facile construction of dense and continuous pillared-layer MOF thin films on a centimeter scale via an aluminum-doped zinc oxide template and hydroxy double salt (HDS) intermediates at room temperature. A series of Cu(II)-based pillared MOFs with different 1,4-benzenedicarboxylic acid (bdc) ligands were explored for optimizing MOF film formation for CO 2 sensor applications. Nonpolar ligands with lower water solubility preferentially formed crystalline pillared MOF structures from HDS intermediates. A Cu 2 (ndc) 2 (dabco) (ndc = 1,4-naphthalene-bdc; dabco = 1,4-diazabicyclo[2.2.2]octane) MOF demonstrated the most dense and uniform film growth with micrometer thickness over one square centimeter area. This synthetic approach for growing Cu 2 (ndc) 2 (dabco) MOF thin films was successfully translated toward two sensing platforms: a quartz crystal microbalance and an optical fiber sensor. These Cu 2 (ndc) 2 (dabco) MOF-coated sensors displayed sensitivity toward CO 2 and response/recovery time on the scale of seconds, even at moderate humidity levels. Finally, this work provides a road map for producing continuous and anisotropic crystalline MOF thin films over a centimeter scale area on various substrates, which will greatly facilitate their utilization in MOF-based sensor devices, among other applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effects of Sucrose on Phase Transitions of Organic/Inorganic Aerosols

Aerosol morphology influences the interactions of particles with light, water uptake, and heterogeneous chemistry. Through these mechanisms, morphology may be important to the role of aerosol particles on the climate system. A factor that impacts morphology is the diverse and complex mixture of organic compounds that make up the aerosol particles in the atmosphere. In this paper, we investigate the effect of sucrose on liquid-liquid phase separation. As the amount of sucrose is increased, the oxygen to carbon ratio (O:C) of the particles increases. We demonstrate that the morphology of the particle changes as O:C is increased with phase separation causing the particle to take on a textured appearance due to large or small inclusions, as opposed to a core-shell particle. As a result of the increased O:C ratio, the separation relative humidity (SRH) of the particles decreases and, in all cases, the SRH can be completely arrested with the addition of a sufficiently large concentration of sucrose. The quantity of sucrose required to arrest phase separation of the particles shows a direct correlation with the SRH of the system without sucrose. The identity of the salt further impacts the amount of sucrose required to arrest phase separation and is controlled more strongly by the identity of the anion. When the mixture contains an organic/inorganic combination that is strongly phase separating, phase separation is observed at an O:C of 0.92 which is a higher O:C value than previously shown (O:C > 0.8). Sucrose is compared with several other high O:C compounds to confirm the influence of the average O:C ratio. In all, these effects could drastically influence aerosol processes in the climate system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Predicting Liquid–Liquid Phase Separation of Submicrometer Proxies for Atmospheric Secondary Aerosol

Liquid–liquid phase separation (LLPS) of atmospheric aerosols can significantly impact climate, air quality, and human health. However, their complex composition, small size, and history-dependent properties result in great uncertainty in the modeling of aerosol phase state and atmospheric processes. Herein, using cryogenic transmission electron microscopy (cryo-TEM), we examined model submicron aerosols composed of organic compounds and ammonium sulfate, and established a parameterization for the separation relative humidity (SRH) that accounts for chemical composition, particle size, and equilibration time. We evaluated different variables that describe chemical composition: O/C ratio, partition coefficient, solubility, molar mass, and polarizability. The O/C ratio fits the SRH of micrometer droplets best, and by using a scaling factor to translate the micrometer SRH parameterization to submicron aerosols, we incorporate the effects of size and equilibration time. The measured scaling factor for the submicron mean SRH (30nm – 1μm, 20 min equilibration times) is 0.80, the factor becomes 1 with equilibration time over 1 hour, and is equal to 0, meaning that SRH is absent, when the aerosol dry diameter is smaller than 30 nm. Furthermore, our parameterization will aid in universal SRH modeling, potentially leading to more accurate predictions of aerosol mass, optical properties, hygroscopicity, and heterogeneous chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiphase Processing of the Water-Soluble and Insoluble Phases of Biomass Burning Organic Aerosol

Biomass burning is one of the most significant sources of organic aerosol in the atmosphere. Biomass burning organic aerosol (BBOA) has been observed to undergo liquid– liquid phase separation (LLPS) to give core–shell morphology with the hydrophobic phase encapsulating the hydrophilic phase, potentially impacting the evolution of light-absorbing components, i.e., brown carbon (BrC), through multiphase processes. Here, we demonstrate how multiphase processing differs between the watersoluble (i.e., hydrophilic) and insoluble (i.e., hydrophobic) phases of BBOA in terms of reactive uptake of ozone in a coated-wall flow tube. Effects of relative humidity (RH) and ultraviolet (UV) irradiation were investigated. Experimental timeseries were used to inform simulations using multilayer kinetic modeling. Among non-irradiated thin films, the uptake coefficient was greatest for the water-soluble phase at 75% RH (3 × 10 –5 , corresponding to a diffusion coefficient of BrC, D BrC , of 3 × 10 –9 cm 2 s –1 ) and least for the same phase at 0% RH (1 × 10 –5 , corresponding to D BrC of 1 × 10 –10 cm 2 s –1 ). The uptake coefficient for the water-insoluble phase fell between these two (about 1.5 × 10 –5 ), regardless of RH, and the corresponding D BrC increased only slightly (8 × 10 –10 cm 2 s –1 at 0% RH to 9 × 10 –10 cm 2 s –1 at 75% RH). The uptake coefficients of both phases at 0% RH decreased significantly after UV irradiation, consistent with a transition from viscous liquid to solid and supported by qualitative microscopy observations. Modeling multiphase ozone oxidation of primary BrC components in the atmosphere demonstrated, first, that LLPS may extend the lifetime of water-soluble BBOA encapsulated by water-insoluble species by a factor of 1.5 at moderate to high RH and, also, that UV irradiation may extend the lifetime of both phases by more than a factor of 2.5.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating Particle Phase State Dependencies during a Historic Pacific Northwest Wildfire Event

The function and lifetime of an atmospheric particle are greatly dependent upon its phase state. Studying particle phase states from specific ambient source types is often challenging due to uncontrolled environmental conditions and multiple source contributions. However, a historic Pacific Northwest wildfire event occurred in September 2020, providing a rare opportunity to study a pseudo-single particle type ambient sample (i.e., wildfire) over time. Sampling was performed in Richland, Washington, capturing aged particles from shifting wildfire sources. In addition to source variability, temporal variation in wildfire particle phase state was observed from single particle analyses. Despite this, single particle elemental compositions were homogenous over time (=87% carbonaceous) with no significant temporal variation in organic functional group abundances within individual particles either (e.g., 4% relative standard deviation in alkene contributions). While particle composition is indeed known to affect phase state, water uptake appeared to be the most significant contributor to phase state variability amongst single particles here, as particle aspect ratios (related to phase state) linearly correlated with ambient relative humidity during sampling (R2 = 0.65). Therefore, while limited to a case study, meteorological considerations are found to convey greater comparative importance than particle composition for aged particle phase state predictions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

π-Extended Porphyrin–Phthalocyanine Heterojunction Devices Exhibiting High Ammonia Sensitivity with a Remarkable Light Effect

π-Extended porphyrins represent an attractive class of organic compounds because of their unique photophysical, optoelectronic, and physicochemical properties. Herein, cross-conjugated (Ace-PQ-Ni) and linear-conjugated (AM6) porphyrins are used to build double-layer heterojunction devices by combining them with a lutetium bisphthalocyanine complex (LuPc 2 ). The heterojunction effect at the porphyrin–phthalocyanine interface plays a key role in the charge transport properties. Both devices exhibit exceptionally high ammonia sensitivity at room temperature and under ambient relative humidity, with limit of detection values of 156 and 115 ppb for Ace-PQ-Ni/LuPc 2 and AM6/LuPc 2 sensors, respectively. Interestingly, the Ace-PQ-Ni/LuPc 2 and AM6/LuPc 2 sensors display opposite effects upon light illumination. While the former sensors show largely decreased ammonia sensitivity under light illumination, the current variation of the latter under ammonia is remarkably enhanced with a multiplication factor of 13 and a limit of detection (LOD) of 83 ppb. Here, the striking difference in their sensing properties upon light illumination is attributed to their different π-conjugation pathways (cross-conjugation versus linear conjugation).

conductometric transducer↗

Incorporating Diurnal and Meter-Scale Variations of Ambient CO 2 Concentrations in Development of Direct Air Capture Technologies

To be implemented on climate-relevant scales, direct air capture of CO 2 (DAC) will require large capital-intensive facilities and careful attention to cost minimization. In making decisions among potential sites for DAC facilities, all of the factors that will impact process cost and efficiency should be considered. In this paper we focus on a factor that has previously received little attention in the DAC community, namely variations in atmospheric conditions on hourly time scales and length scales of meters. We present data curated from extensive previous studies of biosphere-atmosphere fluxes with observations of CO 2 concentration, temperature, and relative humidity (RH) with hourly resolution from many sites in North America. These include locations where typical diurnal variations in CO 2 concentration during summer months exceeds 150 ppm. These variations are larger than the seasonal variations that exist between averaged CO 2 concentrations in winter and summer, and they are highly correlated with diurnal variations in temperature and RH. Diurnal variations are dependent on the height above ground at which CO 2 concentrations are measured, with smaller variations existing at heights of 10 m or more than at ground level. We illustrate the potential implications of these short-term variations for the operation and optimization of a DAC process with process-level calculations for a specific adsorption-based process using amine-rich adsorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Surface Hydration of Porous Nickel Hydroxides Facilitates the Reversible Adsorption of CO 2 from Ambient Air

Direct air capture (DAC) under humid ambient conditions typically requires the use of organic components, with sorbents that are purely inorganic in composition for the most part operating hundreds of degrees above room temperature. In this work, we report porous metal hydroxides as a novel class of water-tolerant, oxidatively and hydrothermally stable low-temperature sorbents that exhibit competitive DAC working capacities of 1.25 mmol/g over 5 consecutive temperature swing adsorption–desorption cycles in the presence of steam and oxygen. Aqueous miscible organic solvent treatments are used to create highly porous structures with surface areas exceeding 700 m 2 /g that capture CO 2 in the form of bicarbonates under dry conditions, and carbonates under wet conditions. Water exerts a facilitative rather than an inhibiting effect on CO 2 binding, and the presence of hydrating multilayers serves to stabilize carbonate species akin to moisture swing adsorbents except for the fact that solvation results in a remarkable (upto 10-fold) increase, not decrease, in DAC capacity. High-valent doping with cerium is used to improve DAC capacities by amplifying surface basicity, evidencing porous nickel hydroxides specifically (and porous metal hydroxides more generally) as a novel class of robust, earth-abundant DAC sorbents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

What Determines the Number and the Timing of Pulses in Afternoon Precipitation in the Green Ocean Amazon (GoAmazon) Observations?

Using GoAmazon observations over the central Amazon, we investigate double-pulse events of afternoon precipitation for the first time. Relative humidity is the dominant factor in determining the onset timing and the number of pulses of precipitation. A moister free troposphere on single-pulse days features heavy precipitation in the early afternoon, which stabilizes the atmosphere and prohibits further convection. On early–onset double-pulse days, weaker precipitation from shallower convection in the first pulse leads to less consumption of atmospheric instability, making the environment favorable for a second pulse of stronger precipitation. A cluster tracking algorithm using the scanning radar reflectivity is developed to examine the relationship between precipitation pulses. Through explicitly tracking convective clusters that exist from the first to the second pulse, convective aggregation plays a more dominant role to the survival of clusters with larger final size, and on average around 20% of cluster survivals are due to natural growth.

54 ENVIRONMENTAL SCIENCES↗

Urban Versus Lake Impacts on Heat Stress and Its Disparities in a Shoreline City

Abstract Shoreline cities are influenced by both urban‐scale processes and land‐water interactions, with consequences on heat exposure and its disparities. Heat exposure studies over these cities have focused on air and skin temperature, even though moisture advection from water bodies can also modulate heat stress. Here, using an ensemble of model simulations covering Chicago, we find that Lake Michigan strongly reduces heat exposure (2.75°C reduction in maximum average air temperature in Chicago) and heat stress (maximum average wet bulb globe temperature reduced by 0.86°C) during the day, while urbanization enhances them at night (2.75 and 1.57°C increases in minimum average air and wet bulb globe temperature, respectively). We also demonstrate that urban and lake impacts on temperature (particularly skin temperature), including their extremes, and lake‐to‐land gradients, are stronger than the corresponding impacts on heat stress, partly due to humidity‐related feedback. Likewise, environmental disparities across community areas in Chicago seen for skin temperature are much higher (1.29°C increase for maximum average values per $10,000 higher median income per capita) than disparities in air temperature (0.50°C increase) and wet bulb globe temperature (0.23°C increase). The results call for consistent use of physiologically relevant heat exposure metrics to accurately capture the public health implications of urbanization.

54 ENVIRONMENTAL SCIENCES↗

Insight the process of hydrazine gas adsorption on layered WS 2 : a first principle study

The process of hydrazine gas adsorption on layered WS 2 has been systematically studied from first principle calculations. Our results demonstrate that this adsorption process is exothermic, and hydrazine molecules are physically adsorbed. The layer-dependent adsorption energy and interlayer separation induced by van der Waals interaction exerted by hydrazine molecules lead to the difficulty in desorbing hydrazine molecules from layered WS 2 as the number of layers increases. The most interesting finding is the emergence of localized impurity states below the Fermi level upon the hydrazine adsorption, irrespective of the number of WS 2 layers, resulting in a significant effect on the band structures and subsequently changing its electrical conductivity. Furthermore, a layer-dependent small charge transfer occurs between hydrazine and layered WS 2 , leading to a charge redistribution and considerable polarization in the adsorbed systems. The existence of defects and the humidity, on the other hand, influences the sensitivity of layered WS 2 to the hydrazine adsorption. Here, obtained results show that a perfectly layered WS 2 might be a promising candidate as an efficient nanosensor to detect such toxic gas in dry environment.

36 MATERIALS SCIENCE↗

Exploring the Performance and Reliability of Screen-Printable Fire-Through Copper Paste on PERC Solar Cells

In this work, we present the performance and reliability of a fire-through copper (Cu) paste which has been screen printed on c-Si solar cell with passivated emitter rear contact (PERC). The Cu paste is fired through silicon nitride (SiN) anti-reflection coating at a peak temperature of 630 degrees C . SEM images of the Cu paste show a Cu core with ~200 nm oxide shell around the particles. This conductive oxide layer acts as a diffusion barrier between Cu and Si and prevents the degradation of cell performance during accelerated aging conditions. An efficiency of 19.250% has been achieved with Voc=654mV,FF= 76.68%, Jsc=38.40 m.A/cm 2 for champion PERC cells. Accelerated testing of the PERC mini-modules in damp heat chamber with 85 degrees C and 85% humidity have demonstrated that the devices are operational even after 1,500 hours. Devices with screen printed Ag contacts on the front side have been studied in parallel to the Cu contacts for comparison.

copper↗

Pangeo-Enabled ESM Pattern Scaling (PEEPS): A customizable dataset of emulated Earth System Model output

Emulation through pattern scaling is a well-established method of rapidly producing climate fields (like temperature or precipitation) from existing Earth System Model (ESM) output that, while inaccurate, is often useful for a variety of downstream purposes. Conducting pattern scaling has historically been a laborious process, in large part due to the increasing volume of ESM output data that has often required downloading and storing locally to train on. Here we describe the Pangeo-Enabled ESM Pattern Scaling (PEEPS) dataset, a repository of trained annual and monthly patterns from CMIP6 outputs. This manuscript describes and validates these updated patterns so that users can save effort calculating and reporting error statistics in manuscripts focused on the use of patterns. The trained patterns are available as NetCDF files on Zenodo for ease of use in the impact community, and are reproducible with the code provided via GitHub in both Jupyter notebook and Python script formats. Because all training data for the PEEPS data set is cloud-based, users do not need to download and house the ESM output data to reproduce the patterns in the zenodo archive, should that be more efficient. Validating the PEEPS data set on the CMIP6 archive for annual and monthly temperature, precipitation, and near-surface relative humidity, pattern scaling performs well over a variety of future scenarios except for regions in which there are strong, potentially nonlinear climate feedbacks. Although pattern scaling is normally conducted on annual mean ESM output data, it works equally well on monthly mean ESM output data. We identify several downstream applications of the PEEPS data set, including impacts assessment and evaluating certain types of Earth system uncertainties.

54 ENVIRONMENTAL SCIENCES↗

Using heterogeneous data to identify signatures of dengue outbreaks at fine spatio-temporal scales across Brazil

Dengue virus remains a significant public health challenge in Brazil, and seasonal preparation efforts are hindered by variable intra- and interseasonal dynamics. Here, we present a framework for characterizing weekly dengue activity at the Brazilian mesoregion level from 2010–2016 as time series properties that are relevant to forecasting efforts, focusing on outbreak shape, seasonal timing, and pairwise correlations in magnitude and onset. In addition, we use a combination of 18 satellite remote sensing imagery, weather, clinical, mobility, and census data streams and regression methods to identify a parsimonious set of covariates that explain each time series property. The models explained 54% of the variation in outbreak shape, 38% of seasonal onset, 34% of pairwise correlation in outbreak timing, and 11% of pairwise correlation in outbreak magnitude. Regions that have experienced longer periods of drought sensitivity, as captured by the “normalized burn ratio,” experienced less intense outbreaks, while regions with regular fluctuations in relative humidity had less regular seasonal outbreaks. Both the pairwise correlations in outbreak timing and outbreak trend between mesoresgions were best predicted by distance. Our analysis also revealed the presence of distinct geographic clusters where dengue properties tend to be spatially correlated. Forecasting models aimed at predicting the dynamics of dengue activity need to identify the most salient variables capable of contributing to accurate predictions. Our findings show that successful models may need to leverage distinct variables in different locations and be catered to a specific task, such as predicting outbreak magnitude or timing characteristics, to be useful. This advocates in favor of “adaptive models” rather than “one-size-fits-all” models. The results of this study can be applied to improving spatial hierarchical or target-focused forecasting models of dengue activity across Brazil.

59 BASIC BIOLOGICAL SCIENCES↗

Microclimate observations associated with snowmelt experiment gradient sites, East River, Colorado, 2017 to 2020

The timing of snowmelt in mountain systems is a main driver of vegetation phenology and production, as well as recharge of soil moisture and ground water. Decreases in maximum snowpack and warmer spring temperatures have led to a higher frequency of early snowmelt. This study combines a natural elevation gradient with an experimental manipulation of snowmelt timing to assess the effect of earlier melt on hillslope and watershed ecohydrological processes. This data package includes csv files with plot and sub-plot level observations of soil temperature (SM_ST.csv), soil moisture (SM_SWC.csv), air temperature (SM_AirT.csv), and relative humidity (SM_rH.csv). The date range of this dataset includes a pre-treatment year (2017), two treatment years (2018 and 2019), and a post-treatment year (2020). Location IDs associated with this data package are: ER-LM, WG-UM, WG-LS, ER-US, and XX-AL. Related data packages include: “Colorado Elevation Gradient Snowmelt Manipulation Plant Phenology 2017-2018” and “Sensor-based phenology from snowmelt experiment gradient, East River, Colorado, 2017 to 2020”

54 ENVIRONMENTAL SCIENCES↗

Integrated Hourly Meteorological Database of 20 Meteorological Stations (1981-2022) for Watershed Function SFA Hydrological Modeling

This dataset contains (a) a script “R_met_integrated_for_modeling.R”, and (b) associated input CSV files: 3 CSV files per location to create a 5-variable integrated meteorological dataset file (air temperature, precipitation, wind speed, relative humidity, and solar radiation) for 19 meteorological stations and 1 location within Trail Creek from the modeling team within the East River Community Observatory as part of the Watershed Function Scientific Focus Area (SFA). As meteorological forcings varied across the watershed, a high-frequency database is needed to ensure consistency in the data analysis and modeling. We evaluated several data sources, including gridded meteorological products and field data from meteorological stations. We determined that our modeling efforts required multiple data sources to meet all their needs. As output, this dataset contains (c) a single CSV data file (*_1981-2022.csv) for each location (20 CSV output files total) containing hourly time series data for 1981 to 2022 and (d) five PNG files of time series and density plots for each variable per location (100 PNG files). Detailed location metadata is contained within the Integrated_Met_Database_Locations.csv file for each point location included within this dataset, obtained from Varadharajan et al., 2023 doi:10.15485/1660962. This dataset also includes (e) a file-level metadata (flmd.csv) file that lists each file contained in the dataset with associated metadata and (f) a data dictionary (dd.csv) file that contains column/row headers used throughout the files along with a definition, units, and data type. Review the (g) ReadMe_Integrated_Met_Database.pdf file for additional details on the script, methods, and structure of the dataset.The script integrates Northwest Alliance for Computational Science and Engineering’s PRISM gridded data product, National Oceanic and Atmospheric Administration’s NCEP-NCAR Reanalysis 1 gridded data product (through the `RCNEP` R package, Kemp et al., doi:10.32614/CRAN.package.RNCEP), and analytical-based calculations. Further, this script downscales the input data into hourly frequency, which is necessary for the modeling efforts.

54 ENVIRONMENTAL SCIENCES↗

SPRUCE Whole Ecosystem Warming (WEW) Environmental Data and Water Table Summaries, Marcell Experimental Forest, Minnesota, 2015-2024

This data set contains observations of photosynthetically active radiation (PAR), precipitation, soil temperature, soil volumetric water content, air temperature, relative humidity, and normalized water table depth that are summarized on a daily, weekly, monthly, and annual basis for each of the SPRUCE plots. Observations span 2015-2024. This dataset draws on several datasets (Hanson et al. 2016; Hanson et al. 2020; and Warren, unpublished data) and compiles these environmental observations into useful formats for data analysis. These environmental metrics can be used to understand the environmental conditions inside SPRUCE environmental chambers throughout the durations of the experiment and can be paired with other data for modeling and analysis. R code used to generate these files is provided as part of the data package. This dataset contains four data files in comma separate (.csv) format and a compressed folder (*.zip) containing three R (*.r) scripts. Additional metadata are provided: one data dictionary and a file-level metadata file in comma separate (.csv) format and a user guide in PDF (*.pdf) format. User note: Users must cite the original dataset/s along with this dataset when publishing any analyses using this dataset. Details on the dataset used to compile each variable are available in the header row of the files and in the user guide.

air temperature↗