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At least 235 records · Page 13

The adsorption of As(V) on poorly crystalline Fe oxyhydroxides, revisited: Effect of the reaction media and the drying treatment

Arsenic (As) adsorbed on Fe oxyhydroxides (adsorbent) is widely occurring in many environmental settings such as in acid mine drainage systems or in the hydrometallurgical operations to form Fe-As coprecipitates. However, the influence of the reaction media and the drying treatment on the microstructure of the directly formed adsorbents at various pHs was still not fully understood. In this work, As adsorption behaviors on various forms of Fe oxyhydroxides were systematically investigated by using XRD, FTIR, Raman, XANES, and HRTEM. Overall, the results revealed that at weak acidic pH, more As could adsorbed on the suspension adsorbent formed in sulfate and chloride media than that in nitrate media, possibly due to the microstructure alteration of the adsorbent in the presence of sulfate and chloride. Besides, the increasing crystallinity of the Fe oxyhydroxides and the aggregation effect after drying were the major reasons why less As could be hold by the dried adsorbents than that of the corresponding suspension adsorbents. These findings could shed more light on the nature of the Fe oxyhydroxides which may be helpful for more precisely predicting the fate of some toxic metal(loid)s in the environment.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular structures of dissolved and colloidal As V –Fe III complexes and their roles in the mobilization of As V under strongly acidic conditions

The effect of high concentration of iron (Fe III ) on the speciation and mobility of arsenic (As) under strongly acidic conditions remains unclear. This work studied the redistribution and speciation of As V and Fe III at Fe/As molar ratio of 1–14 and pH 1.5–2.0 in the dissolved, colloidal, and solid phases. Results showed that the elevated Fe III induced the decomposition of the precipitated poorly crystalline ferric arsenate by forming dissolved (< 3 kDa) and colloidal (3 kDa–0.1 µm) As–Fe complexes. The fraction of particulate As (> 0.1 µm) decreased from 70–90% to less than 20% when the Fe/As molar ratio increased from 1 to 14. The particle size of the bulk samples decreased significantly with the increase of Fe III concentration. The FTIR results suggested that AsV in dissolved/colloidal As–Fe complexes dominantly occurred as HAsO 4 2– species. The EXAFS results indicated that each HAsO 4 2– coordinated with approximately two Fe atoms in dissolved/colloidal As–Fe complexes at Fe/As ≥ 2. Furthermore, the findings suggest that high aqueous Fe III concentration can promote the mobility of As by forming dissolved/colloidal Fe–As complexes in acidic waters, potentially accelerating As transport from source to downstream in acid mine drainage systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Microbiological and geochemical characterization of As-bearing tailings and underlying sediments

Over the past 100 years, extensive oxidation of As-bearing sulfide-rich tailings from the abandoned Long Lake Gold Mine (Canada) has resulted in the formation of acid mine drainage (pH 2.0-3.9) containing high concentrations of dissolved As (similar to 400 mg L -1 ), SO 4 2- , Fe and other metals. Dissolved As is predominantly present as As(III), with increased As(V) near the tailings surface. Pore-gas O 2 is depleted to < 1 vol% in the upper 30-80 cm of the tailings profile. The primary sulfides, pyrite and arsenopyrite, are highly oxidized in the upper portions of the tailings. Elevated proportions of sulfide-oxidizing prokaryotes are present in this zone (mean 32.3% of total reads). The tailings are underlain by sediments rich in organic C. Enrichment in δ 34 S-SO 4 in pore-water samples in the organic C-rich zone is consistent with dissimilatory sulfate reduction. Synchrotron-based spectroscopy indicates an abundance of ferric arsenate phases near the impoundment surface and the presence of secondary arsenic sulfides in the organic-C beneath the tailings. The persistence of elevated As concentrations beneath the tailings indicates precipitation of secondary As sulfides is not sufficient to completely remove dissolved As. The oxidation of sulfides and release of As is expected to continue for decades. The findings will inform future remediation efforts and provide a foundation for the long-term monitoring of the effectiveness of the remediation program.

54 ENVIRONMENTAL SCIENCES↗

A new soil mixing layer model for simulating conservative solute loss from initially saturated soil to surface runoff

Surface water pollution due to solute loss from soil to surface runoff is a serious threat to the environment, and it is of great significance to predict the solute loss. While soil mixing layer theory has been widely used to predict the solute loss, it has been observed that the conventional soil mixing layer models with constant mixing layer depth underestimate solute concentration in surface runoff, and thus underestimate the solute loss after surface runoff starts. This study introduced a new soil mixing layer model with a new concept that the mixing layer depth increases downward with time after surface runoff occurs. This new concept was implemented by adding a mixing front between the soil mixing layer and its underlying soil layer, which is conceptually similar to the wetting front of soil infiltration given by the Green-Ampt equation. This is equivalent to treating the soil mixing layer as a deforming control volume. A mechanistic explanation for the new model was presented. This study also developed a closed form solution of the new model. The new model was evaluated by simulating five laboratory experiments conducted by two groups of researchers. The first two experiments have ponding water, and consider different drainage and runoff conditions at both early and late runoff times. The other three experiments do not have ponding water, and consider different infiltration conditions at the bottom of soil boxes. Simulation results of the five experiments show that the new model resolves the underestimation problem of conventional soil mixing layer models. The new model is subject to a total of six limits such as that the new model only considers conservative solute. Three limits are related to the assumptions used to derive the closed form solution, and they may be alleviated in a future research as briefly discussed at the end of the paper.

54 ENVIRONMENTAL SCIENCES↗

Dynamic coevolution of baseflow and multiscale groundwater flow system during prolonged droughts

Field and numerical studies suggest that baseflow is composed of waters from a spectrum of groundwater flow paths termed the Groundwater Flow System (GWFS) – from shallow hillslope contributions to watershed-scale deep circulation originating in headwaters and discharging into lowland rivers. Here, we explore the evolution of the GWFS under prolonged droughts to understand its dynamics and multiscale nature, and to elucidate its role in baseflow generation and recession at the watershed scale. In this work, we consider three drought scenarios of varying severity and simulate groundwater flow in a 2-D cross-section of an idealized watershed with deep permeable bedrock, tracking the evolution of flow paths, baseflow, and residence times during the recession process. We find that baseflow generation at different drainage stages, and within different subwatersheds, is influenced distinctly by flow paths of different scales, depending on the relative strength of the flow paths and the position of the subwatersheds relative to the recharge/discharge zones of the deeper watershed-scale groundwater circulation. Despite having the same local relief, geology, and climate, baseflow from each subwatershed has a distinct recession behavior and time-dependent residence time distribution. Also, the hydraulic and transport characteristics of baseflow generation co-evolve and are strongly affected by the connection state of the water table to subwatersheds. These findings suggest that asynchrony and dissimilarity of baseflow generation from hillslopes under the impact of the watershed-scale groundwater flow, and interactions with local-scale and intermediate-scale groundwater flow, must be taken into account when interpreting baseflow recession data and building conceptual baseflow models at the watershed scale.

54 ENVIRONMENTAL SCIENCES↗

Forecasting Multi-Step-Ahead Street-Scale Nuisance Flooding using a seq2seq LSTM Surrogate Model for Real-Time Application in a Coastal-Urban City

In coastal-urban cities facing an elevated risk of nuisance flooding (by rain and tide) due to increased heavy rainfall, sea level rise, urbanization, and aging drainage systems, real-time flood forecasting at the street-scale can provide useful information to transportation decision-makers. Physics-Based Models (PBMs) that offer high accuracy come with high computational runtimes and costs that limit their application for real-time flood forecasting. To address this challenge, Machine Learning (ML) surrogate models trained from PBMs have been proposed to provide street-scale flood forecasts. Previous related studies have focused on using Long Short-Term Memory (LSTM) architectures to model hourly flood depth on streets. While LSTM models can capture input sequences effectively, they fall short in accurately preserving output sequences, limiting their suitability for multi-step-ahead forecasts. The seq2seq LSTM architecture offers a key advantage here by capturing the full sequence of input–output, making it potentially more suitable for multi-step-ahead flood forecasts compared to traditional LSTM models. However, seq2seq LSTM has not been tested for street-scale flood forecasting, particularly for rapidly fluctuating nuisance flooding events which require special attention to its temporal sequences. Hence, in this study, we applied the seq2seq LSTM model to explore multi-step-ahead street-scale nuisance flooding and compared its results to the traditional LSTM model as a benchmark model. LSTM and seq2seq LSTM surrogate models were applied to 22 flood-prone streets in Norfolk, Virginia, as a case study with a 4-hr (short-term) and 8-hr (long-term) lead time. The models were trained with environmental (rainfall and tide) and topographic (elevation, Topographic Wetness Index, and Depth-To-Water) features along with PBM-derived water depths for different storm events. The results demonstrated satisfactory performance of both LSTM and seq2seq LSTM surrogate models throughout the forecast period compared to the PBM. However, the seq2seq LSTM showed lower Mean Absolute Error (MAE)/ Root Mean Square Error (RMSE) and higher Nash–Sutcliffe Efficiency (NSE)/ correlation than the LSTM across most lead times, particularly for long-term forecasting due to its supremacy in handling both input–output sequences together, which is missing in the traditional LSTM. For example, in the long-term, the average RMSE ranges were 0.0268–0.0373 m for LSTM and 0.0226–0.0319 m for seq2seq LSTM, while in the short-term, they were 0.0263–0.0293 m and 0.0261–0.0283 m, respectively. Additionally, while both models exhibited similar performance in distinguishing flooded and non-flooded streets for flood depth ≥ 0.1 m, the seq2seq LSTM model demonstrated superior performance for higher flood depths (such as ≥ 0.2 m and ≥ 0.3 m). Once trained, inference took only 0.09 to 0.11 s (short-term) and 0.30 to 0.35 s (long-term) per storm event for the 22 streets, making the application highly suitable for real-time decision-making during nuisance flood events.

54 ENVIRONMENTAL SCIENCES↗

Urban wash-off of tire wear particles

Tire wear particles (TWPs) are an important class of microplastics due to their toxicity and abundance. Because most TWPs are generated on impervious road surfaces, urban wash-off is the critical first phase of waterborne transport from their zone of production to stormwater drainage. However, little is known about the driving factors behind their mobilization. In this study, we use a rainfall simulator to investigate how surface roughness, rainfall intensity, and surface slope affect wash-off behaviors of TWPs. We also analyze how the size and shape of mobilized TWPs change over the course of simulated storm events. We found that low surface roughness, high rainfall intensity (most significant factor), and low slope result in the most rapid conveyance of TWP load. On average, large particles (>1000 µm) travelled faster than small particles (<125 µm). Particle shape explained a very small amount of variance in TWP wash-off velocity but was found to be more important under higher surface roughness conditions. In addition to wash-off velocity, we found similar conditions controlled the percent mobilization of TWPs. Low surface roughness and high rainfall intensity resulting in higher TWP wash-off rates is consistent with mineral sediment wash-off behavior. Conversely, low surface slope and large particle size leading to faster conveyance is directly opposed to mineral sediment wash-off. Our findings suggest drag-dominated flow and that sufficient runoff depth is the most important parameter governing TWP wash-off. These findings are important first steps to understanding wash-off behaviors of TWPs and informing future modeling efforts and mitigation strategies.

13 HYDRO ENERGY↗

Systematic Evaluation of Atmospheric Forcing, Surface Datasets, and Mesh Effects on Kilometer-Scale Land Surface and River Modeling

Earth system models are advancing toward kilometer-scale resolution to capture local climate impacts and extremes. High-resolution land and river modeling depends on multiple factors, including mesh, surface datasets, and atmospheric forcing, but their relative effects at kilometer scales remain unquantified. We evaluated five Energy Exascale Earth System Model land and river configurations over the Mid-Atlantic region using two mesh (1/8° structured versus variable-resolution unstructured mesh), two surface datasets (default versus newly developed), and three atmospheric forcings (NLDAS2, MSWX, GSWP). Evaluation against satellite, reanalysis, and in situ benchmarks across water, energy, and carbon cycles quantifies how these factors affect model performance. Forcing selection produces the largest bias reductions (12-99% across variables), followed by surface datasets (7-75%) and mesh (up to 21%). Forcing effects vary by variable, with MSWX reducing biases for snow water equivalent, evapotranspiration, albedo, temperature, and gross primary productivity, GSWP for snow cover and runoff, and NLDAS for soil moisture and streamflow. The use of newly developed surface datasets improves gross primary productivity (58% bias reduction) and evapotranspiration but increase soil moisture and albedo biases due to current modeling limitations. Variable-resolution unstructured mesh improves the simulation of small-basin streamflow through better capturing drainage networks, though mesh minimally affects other land variables. These findings provide important guidance for high-resolution modeling development and actionable science.

Land and River modeling↗

A review study of rare Earth, Cobalt, Lithium, and Manganese in Coal-based sources and process development for their recovery

The world’s majority predominantly relies on foreign sources for supplying critical minerals. This renders the countries susceptible to supply chain disruption and urges them to develop alternative sources to compete in technological advancements. Among many proven newly identified sources, coal and coal-based materials present their opportunities. Due to the complex structure of coal, many mineral forms can be found in coal-related sources, including critical element-containing minerals. Among the fifty critical elements and minerals defined by the USGS, the rare earth elements, cobalt, lithium, and manganese, are particularly significant as they have enormous importance in high-technology product development. These critical metals can be found in high concentrations in coal-derived sources, such as coal refuse, coal combustion products, and coal acid mine drainage, and be recovered through various separation techniques. Further, this study aims to advance the understanding of these elements' extraction and commercial potential from coal and coal-related sources and help address the world's challenges in the critical mineral supply chain. The concentrations and occurrences of these four commodities in coal-related sources were first reviewed. Later, their recovery processes were discussed, and a conceptual process flowsheet was proposed to selectively recover the rare earth elements, lithium, cobalt, and manganese from coal-based sources.

58 GEOSCIENCES↗

Controls on reservoir properties in organic-matter-rich shales: Insights from MICP analysis

Mercury injection capillary pressure (MICP) analysis was used to study organic-matter-rich Devonian shales varying in maturity from marginally mature to postmature to discuss controls on drainage and imbibition in shale reservoirs. Six samples come from the New Albany Shale; their total organic carbon (TOC) ranged from 3.3–8.4 % and vitrinite reflectance (R o ) from 0.54–1.42 %. One Marcellus Shale sample with R o 2.50 % was used to extend the maturity range to the advanced dry gas window. Three coal samples of varying rank were also included for comparison. Porosity of the shales ranges from 1.5–5.0 %, and MICP-derived permeability ranges from 0.17–9.9 mD. Injection capillary pressure curves have a range of entry pressures from 0.055 to0.421 MPa, and no relationship of entry pressure with maturity was revealed. Maturity, however, has an influence on pore size distribution, with the higher-maturity samples having significantly lower volumes of pores with throats less than 10 nm in diameter. Withdrawal capillary pressure curves document a wide range of withdrawal efficiencies from 55 % to almost 100 %, and pores having throats between 3–50 nm in diameter play a major role in the ability of mercury to be released from the pore system. The obtained data provide valuable information about shale properties and their behavior not only in the air-mercury system but also under reservoir conditions.

02 PETROLEUM↗

Chronostratigraphy of talus flatirons and piedmont alluvium along the Book Cliffs, Utah – Testing models of dryland escarpment evolution

Research on the evolution of dryland escarpments and what drives and controls their erosional retreat have been limited by a lack of chronologically constrained records. Prior investigations of escarpments in the southwestern U.S. and globally garner two endmember conceptual models -- one focused on bottom-up baselevel drivers and autogenic variations in piedmont and toeslope erosion processes, the other focused on the role of climate as a top-down forcing mechanism on sediment production and transport from cliffs. In this work, we test these conceptual models along a section of the Book Cliffs in central Utah, where climate has varied strongly and baselevel has fallen significantly over the late Quaternary. Four generations of talus flatirons and piedmont terraces are preserved in the study area we date them by optically stimulated luminescence and 10Be-exposure techniques. OSL depositional ages cluster into four generations of deposits with mean ages and mean standard errors of 117.8 ± 6.7 ka, 83.4 ± 3.3 ka, 52.4 ± 1.8 ka, and 5.6 ± 0.3 ka. 10Be-exposure results from talus boulders protruding from flatirons confirm that the youngest generation of talus is Holocene, with recent rock-fall boulders still being received on the landform top. Older flatiron generations produce incoherent, minimum exposure ages reflecting an increasing dominance of in situ boulder weathering and a steady-state denudation rate of ~45 mm/ky after tens of thousands of years. Based on the chronostratgraphy and correlation of talus and piedmont deposits, we interpret climate as the primary control on escarpment evolution. Depositional ages do not correspond to glacial epochs as historically presumed, but instead to episodes of intermediate and unstable or variable Pleistocene climate during Marine Isotope Stage-3 and 5 a/b. Results support the significance of high climate variability at millennial timescales in driving both sediment production by mass wasting from the cliff as well as sediment storage and reworking along the piedmont. In contrast, wetter climates of glacial epochs apparently caused greater erosion and sediment transport to trunk drainages. Our chronology also reveals a systematic decrease in deposit age with increasing distance up the piedmont from the regional baselevel of the Price River, consistent with transient fluvial incision and terrace abandonment. The Book Cliffs record notably does not correlate with similarly constrained records in Spain or the contrasting record from the Negev, yet they all share the feature of enhanced talus deposition and cliff retreat corresponding to climate instability rather than in response to steady glacial-climate conditions. Thus, we outline a model of escarpment evolution and retreat governed largely by top-down climate-forcing of sediment production and transport during climate variability, with local changes in baselevel and erosional processes on the piedmont being a modifying, secondary factor.

58 GEOSCIENCES↗

Improved signal stability in inductively coupled plasma–atomic emission spectrometry through use of tandem spray chambers and surfactant addition

A search for causes of intermittent mid-term (about two hours) instability in emission signals from an inductively coupled plasma led to adoption of a tandem spray-chamber arrangement and subsequently to use of a surfactant (Triton X-100) to mitigate the remaining and newly found instabilities. Through a series of investigations, abrupt signal excursions in the tandem setup were traced to droplet coagulation and drainage inside the glass tube that connected the two spray chambers. However, the signal shifts were not the result of sample-solution release directly but rather to the influence of the underlying factors on plasma behavior. Experiments tailored to the study included not only examination of temporal signal behavior but also collection of long-term videos and measurement of radiofrequency characteristics of the plasma. The addition of a surfactant, Triton X-100, for signal-stability improvement is applicable not only to systems that employ tandem spray chambers but also to conventional single Scott-type chamber arrangements. Further, use of the surfactant was unsuccessful in overcoming “acid effects”, either of the steady-state or transient nature, and did not alter plasma background or analyte signals significantly.

Inductively coupled plasma–atomic emission spectro↗

An ICP-OES method for the precise and accurate quantification of rare earth elements in natural water: A comparative study from mine waste sites in New Mexico, USA

Inductively coupled plasma techniques such as ICP-OES and ICP-MS are routinely used to determine the concentrations of rare earth elements (REE) in water samples. However, their performance for the determination of REE concentration in mine drainage waters from epithermal vein and porphyry copper mining districts has not been evaluated extensively. In this work, we develop an REE analysis method on an Agilent 5900 ICP-OES instrument and assess the accuracy and precision for the quantification of REE in the natural waters collected from mine adits and an acid seep of mine sites in the Steeple Rock and Hillsboro mining districts, New Mexico, USA. The total REE concentrations in the water samples were measured using the methods we developed for both ICP-OES and ICP-MS. The power of the new ICP-OES method lies in routine analysis of μg/L level concentrations normally analyzed using ICP-MS, including a U.S. Geological Survey standard reference sample, laboratory blank samples spiked with a National Institute of Standards and Technology traceable standard, and surface water samples from mine waste sites. This ICP-OES method achieves low quantification limits ranging from 0.2 to 5 μg/L and excellent analytical accuracy and precision for REE analysis. The precision of light (La-Gd) and heavy (Tb-Lu) REE analysis using this method are better than 5% at average concentrations above 5 ± 4 μg/L and 3 ± 2 μg/L, respectively, and 3% at average concentrations above 10 ± 9 μg/L and 5 ± 4 μg/L, respectively. This method also shows excellent sensitivity and reproducibility for our laboratory and field samples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamic Surface Incorporation of Pb 2+ Ions at the Actively Dissolving Calcite (104) Surface

The reaction of dissolved Pb 2+ with calcite surfaces at near-equilibrium conditions involves adsorption of Pb 2+ and precipitation of secondary heteroepitaxial Pb-carbonate minerals. A more complex behavior is observed under far-from-equilibrium conditions, including strong inhibition of calcite dissolution, development of microtopography, and near-surface incorporation of multiple monolayers (ML) of Pb 2+ without precipitation of secondary phases [where 1 ML ≡ 1 Ca/20.2 Å 2 , the crystallographic site density of the calcite (104) lattice plane]. However, the mechanistic controls governing far-from-equilibrium reactivity are not well understood. Here, in this study, we observe the interfacial incorporation of dissolved Pb 2+ during the dissolution of calcite (104) surfaces at pH ~3.7 in a flow-through reaction cell, revealing the formation of a ~1 nm thick Pb-rich calcite layer with a total Pb coverage of ~1.4 ML. These observations of the sorbed Pb distribution used resonant anomalous X-ray reflectivity, X-ray fluorescence, and nanoinfrared atomic force microscopy. We propose that this altered surface layer represents a novel sorption mode that is stabilized by conditions of sustained disequilibrium. This behavior may significantly impact the transport of dissolved metals during disequilibrium processes occurring in acid mine drainage and subsurface CO 2 injection and, if appropriately accounted for, could improve the predictive capability of geochemical reactive-transport models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Seasonal Controls on Microbial Depolymerization and Oxidation of Organic Matter in Floodplain Soils

Floodplain soils are vast reservoirs of organic carbon often attributed to anaerobic conditions that impose metabolic constraints on organic matter degradation. What remains elusive is how such metabolic constraints respond to dynamic flooding and drainage cycles characteristic of floodplain soils. Here, in this work, we show that microbial depolymerization and respiration of organic compounds, two rate-limiting steps in decomposition, vary spatially and temporally with seasonal flooding of mountainous floodplain soils (Gothic, Colorado, USA). Combining metabolomics and -proteomics, we found a lower abundance of oxidative enzymes during flooding coincided with the accumulation of aromatic, high-molecular weight compounds, particularly in surface soils. In subsurface soils, we found that a lower oxidation state of carbon coincided with a greater abundance of chemically reduced, energetically less favorable low-molecular weight metabolites, irrespective of flooding condition. Our results suggest that seasonal flooding temporarily constrains oxidative depolymerization of larger, potentially plant-derived compounds in surface soils; in contrast, energetic constraints on microbial respiration persist in more reducing subsurface soils regardless of flooding. Our work underscores that the potential vulnerability of these distinct anaerobic carbon storage mechanisms to changing flooding dynamics should be considered, particularly as climate change shifts both the frequency and extent of flooding in floodplains globally.

54 ENVIRONMENTAL SCIENCES↗

Biogeochemical Controls on Wood Degradation as a Source of Bioavailable Carbon in Denitrifying Bioreactors

Woodchip bioreactors (WBRs) are important tools for the removal of nitrate in agricultural drainage, but their effectiveness is often limited by the slow degradation of lignocellulosic wood residues into bioavailable forms of carbon that fuel denitrifying microorganisms. Here, we examine biogeochemical factors regulating wood degradation in saturated woodchip beds, with a focus on the effects of dissolved oxygen (DO), iron (Fe), and manganese (Mn) in generating oxidative activity that can enhance wood decomposition. Woodchips from a 10-year-old WBR were characterized with bulk techniques and a novel combination of μX-ray scattering, μXRF, and μXANES to visualize the depletion of crystalline cellulose as a proxy for wood degradation. Woodchips from upstream portions of the reactor exhibited the greatest degradation, probably due to greater DO exposure, and degradation was localized to a 100 to 200 μm thick surface layer that was also associated with higher concentrations of Fe and Mn. Greater degradation was associated with faster nitrate removal. μXANES analysis of Fe and Mn in the surface layer indicated the presence of a microenvironment in which oxygenation reactions of Fe(II) and Mn(II) could contribute to the formation of reactive oxidants involved in the degradation of lignocellulose. In conclusion, our results provide new insight into biogeochemical properties that influence wood decomposition in WBRs at both micro- and macroscales and how these wood degradation processes are coupled with denitrification.

36 MATERIALS SCIENCE↗

Extreme Antiscaling Performance of Slippery Omniphobic Covalently Attached Liquids

Scale formation presents an enormous cost to the global economy. Classical nucleation theory dictates that to reduce the heterogeneous nucleation of scale, the surface should have low surface energy and be as smooth as possible. Past approaches have focused on lowering surface energy via the use of hydrophobic coatings and have created atomically smooth interfaces to eliminate nucleation sites, or both, via the infusion of low-surface-energy lubricants into rough superhydrophobic substrates. Although lubricant-based surfaces are promising candidates for antiscaling, lubricant drainage inhibits their utilization. Here, we develop methodologies to deposit slippery omniphobic covalently attached liquids (SOCAL) on arbitrary substrates. Similar to lubricant-based surfaces, SOCAL has ultralow roughness and surface energy, enabling low nucleation rates and eliminating the need to replenish the lubricant. To enable SOCAL coating on metals, we investigated the surface chemistry required to ensure high-quality functionalization as measured by ultralow contact angle hysteresis (<3°). Using a multilayer deposition approach, we first electrophoretically deposit (EPD) silicon dioxide (SiO 2 ) as an intermediate layer between the metallic substrate and SOCAL. The necessity of EPD SiO 2 is to smooth (<10 nm roughness) as well as to enable the proper surface chemistry for SOCAL bonding. To characterize antiscaling performance, we utilized calcium sulfate (CaSO 4 ) scale tests, showing a 20× reduction in scale deposition rate than untreated metallic substrates. Descaling tests revealed that SOCAL dramatically decreases scale adhesion, resulting in rapid removal of scale buildup. Furthermore, our work not only demonstrates a robust methodology for depositing antiscaling SOCAL coatings on metals but also develops design guidelines for the creation of antifouling coatings for alternate applications such as biofouling and high-temperature coking.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Polyelectrolyte Complex Coacervate Assembly with Cellulose Nanofibers

Polyelectrolytes are used in paper manufacturing to increase flocculation and water drainage and improve mechanical properties. In this study, we examine the interaction between charged cellulosic nanomaterials and polyelectrolyte complex coacervates of weak polyelectrolytes, polyacrylic acid salt, and polyallylamine hydrochloride. We observe that by changing the order of addition of the polyelectrolytes to cellulose nanofibers (CNFs), we can tune the interactions between the materials, which in turn changes the degree of association of the coacervates to the CNFs and the rate at which they aggregate. Importantly for the papermaking process, when adding the polyelectrolytes sequentially to the CNFs, we found faster aggregation to the fibers and lower water retention values compared to those when preformed coacervates or CNFs by themselves were used. Coarse-grain molecular dynamic simulations further support the fundamental mechanism of aggregation by taking into consideration the interaction between cellulose and the complexes at the molecular level. The simulations corroborate the experimental observations by showing the importance of strong electrostatic interactions in aggregate formation.

36 MATERIALS SCIENCE↗