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At least 19 records

Understanding supercooling mechanism in sodium sulfate decahydrate phase-change material

Salt hydrate-based phase-change materials are considered promising for future heat storage applications in residential heating/cooling systems. Smooth phase transition from the liquid to solid phase and vice versa is essential for effective heat exchanger; however, supercooling in salt hydrates delays the onset of liquid–solid phase transition. We investigate the molecular level mechanism of supercooling in sodium sulfate decahydrate (SSD). SSD is a complex salt hydrate whose properties are governed by electrostatic forces that include pure Coulombic interactions as well as hydrogen bonds. Experimentally, we examine the importance of a nucleator in reducing supercooling temperatures. We investigated the effect of various mass concentrations of a borax nucleator on a decrease of supercooling temperatures. Molecular dynamics simulation techniques are used to obtain a basic understanding of supercooling in SSD. We observe that by introducing borax as a nucleator, there is a decrease in the supercooling temperature before nucleation. Our molecular dynamics simulations show that long-range electrostatics between sodium and sulfate ion pairs and that with polar water molecules is responsible for delayed nucleation in SSD that results in supercooling, and also, dynamics of charged molecules slows down. The lack of crystallization leads to amorphous structures in supercooled SSD.

36 MATERIALS SCIENCE↗

Reversible structural transformations in supercooled liquid water from 135 to 245 K

Water has many anomalous properties compared to “simple” liquids, and these anomalies are typically enhanced in supercooled water.1-3 While numerous models have been proposed, including the liquid-liquid critical point,4,5 the singularity-free scenario,6 and the stability limit conjecture,1 a molecular-level understanding remains elusive. The main difficulty in determining which, if any, of these models is correct is the limited amount of data in the relevant temperature and pressure ranges. For water at ambient pressures, which is the focus of this work, data is largely missing from 160 – 232 K (“No Man’s Land”) due to rapid crystallization.2,3 Whether rapid crystallization is just an experimental obstacle, or a fundamental problem signaling the inability of water to thermally equilibrate prior to crystallization is also a major unanswered question.5,7 Here, we investigate the structural transformations of transiently-heated, supercooled water with nanosecond time resolution using infrared vibrational spectroscopy. The experiments demonstrate three key results. First, water’s structure relaxes from its initial configuration to a “steady-state” configuration prior to the onset of crystallization over a wide temperature range. Second, water’s steady-state structure can be reproduced by a linear combination of two, temperature-independent structures that correspond to a “high-temperature liquid” and a “low-temperature liquid.” Third, the observed structural changes are reversible over the full temperature range. Taken together, these results show that supercooled water can equilibrate prior to crystallization for temperatures from the homogeneous nucleation temperature, TH ~232 K,3 down to the glass transition temperature (Tg ~ 136 K). Second, the results provide support for the hypothesis that supercooled water can be described as a mixture of two, structurally-distinct, interconvertible liquids from 135 K to 245 K.5,8-18

Kringle, Loni M.↗

Demonstration of neutron radiation-induced nucleation of supercooled water

In this study, we present direct evidence for neutrons causing nucleation of supercooled water. Highly purified water (20 nm filtration) is cooled to well below freezing (as low as −20 °C) with a radioactive calibration source of neutrons/gamma-rays either present or removed during each of many control cooling runs for the same volume of water. When it is primarily neutrons irradiating the sample bulk, the non-equilibrium freezing point (also known as the “supercooling point”) is, on average, +0.7 °C warmer than the control equivalent, with a statistical significance of greater than 5 Sigma, with systematic uncertainty included. This effect is not observed with water in the presence of gamma-rays instead of neutrons. While these neutrons should have theoretically had sufficient energy to mount the energy barrier, corroborating our results, their raising of supercooling temperature has never been reported experimentally to the best of our knowledge. The potential to use deeply supercooled solutions, not only water, as metastable detectors for radiation and perhaps dark matter or neutrino physics presents now a new avenue for exploration.

Szydagis, Matthew↗

Anomalies and Local Structure of Liquid Water from Boiling to the Supercooled Regime as Predicted by the Many-Body MB-pol Model

For the past 50 years, researchers have sought molecular models that can accurately reproduce water’s microscopic structure and thermophysical properties across broad ranges of its complex phase diagram. Herein, molecular dynamics simulations with the many-body MB-pol model are performed to monitor the thermodynamic response functions and local structure of liquid water from the boiling point down to deeply supercooled temperatures at ambient pressure. The isothermal compressibility and isobaric heat capacity show maxima near 223 K, in excellent agreement with recent experiments, and the liquid density exhibits a minimum at ~208 K. A local tetrahedral arrangement, where each water molecule accepts and donates two hydrogen bonds, is found to be the most probable hydrogen-bonding topology at all temperatures. Further, this work suggests that MB-pol may provide predictive capability for studies of liquid water’s physical properties across broad ranges of thermodynamic states, including the so-called water’s “no man’s land” which is difficult to probe experimentally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structural changes across thermodynamic maxima in supercooled liquid tellurium: a water-like scenario

Liquid polymorphism is an intriguing phenomenon which has been found in a few single-component systems, the most famous being water. By supercooling liquid Te to more than 130 K below its melting point and performing simultaneous small-angle and wide-angle X-ray scattering measurements, we observe clear maxima in its thermodynamic response functions around 615 K, suggesting the possible existence of liquid polymorphism. A close look at the underlying structural evolution shows the development of intermediate-range order upon cooling, most strongly around the thermodynamic maxima, which we attribute to bond-orientational ordering. The striking similarities between our results and those of water, despite the lack of hydrogen-bonding and tetrahedrality in tellurium, indicate that water-like anomalies may be a general phenomenon among liquid systems with competing bond- and density-ordering.

36 MATERIALS SCIENCE↗

The prevalence of precipitation from polar supercooled clouds

Abstract. Supercooled clouds substantially impact polar surface energy budgets, but large-scale models often underestimate their occurrence, which motivates accurately establishing metrics of basic processes. An analysis of long-term measurements at Utqiaġvik, Alaska, and McMurdo Station, Antarctica, combines lidar-validated use of soundings to identify supercooled cloud layers and colocated ground-based profiling radar measurements to quantify cloud base precipitation. We find that more than 85 % (75 %) of sampled supercooled layers are precipitating over the Arctic (Antarctic) site, with more than 75 % (50 %) precipitating continuously to the surface. Such high frequencies can be reconciled with substantially lesser spaceborne estimates by considering differences in radar hydrometeor detection sensitivity. While ice precipitation into supercooled clouds from aloft is common, we also find that the great majority of supercooled cloud layers without ice falling into them are themselves continuously generating precipitation. Such sustained primary ice formation is consistent with continuous activation of immersion-mode ice-nucleating particles (INPs), suggesting that supercooled cloud formation is a principal gateway to ice formation at temperatures greater than ∼-38 ∘C over polar regions. The prevalence of weak precipitation fluxes is also consistent with supercooled cloud longevity and with well-observed and widely simulated case studies. An analysis of colocated microwave radiometer retrievals suggests that weak precipitation fluxes can be nonetheless consequential to moisture budgets for supercooled clouds owing to small liquid water paths. The results here also demonstrate that the observed abundance of mixed-phase clouds can vary substantially with instrument sensitivity and methodology. Finally, we suggest that these ground-based precipitation rate statistics offer valuable guidance for improving the representation of polar cloud processes in large-scale models.

54 ENVIRONMENTAL SCIENCES↗

Dynamic Heterogeneity and Kovacs’ Memory Effects in Supercooled Water

Understanding the properties of supercooled water is important for developing a comprehensive theory for liquid water and amorphous ices. Because of rapid crystallization for deeply supercooled water, experiments on it are typically carried out under conditions in which the temperature and/or pressure are rapidly changing. As a result, information on the structural relaxation kinetics of supercooled water as it approaches (metastable) equilibrium is useful for interpreting results obtained in this experimentally challenging region of phase space. Here, we used infrared spectroscopy and the fast time resolution obtained by transiently heating nanoscale water films to investigate relaxation kinetics (aging) in supercooled water. When the structural relaxation of the water films was followed using a temperature jump protocol analogous to the classic experiments of Kovacs, similar memory effects were observed. In particular, after suitable aging at one temperature, water’s structure displayed an extremum versus the number of heat pulses upon changing to a second temperature before eventually relaxing to a steady-state structure characteristic of that temperature. A random double well model based on the idea of dynamic heterogeneity in supercooled water accounts for the observations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly supercooled riming and unusual triple-frequency radar signatures over McMurdo Station, Antarctica

Abstract. Riming of ice crystals by supercooled water droplets is an efficient ice growth process, but its basic properties are still poorly known. While it has been shown to contribute significantly to surface precipitation at mid-latitudes, little is known about its occurrence at high latitudes. In Antarctica, two competing effects can influence the occurrence of riming: (i) the scarcity of supercooled liquid water clouds due to the extremely low tropospheric temperatures and (ii) the low aerosol concentration, which may lead to the formation of fewer and larger supercooled drops potentially resulting in an enhanced riming efficiency. In this work, by exploiting the deployment of an unprecedented number of multiwavelength remote sensing systems (including triple-frequency radar measurements) in West Antarctica, during the Atmospheric Radiation Measurements West Antarctic Radiation Experiment (AWARE) field campaign, we evaluate the riming incidence at McMurdo Station and find that riming occurs at much lower temperatures when compared to previous results in the mid-latitudes. This suggests the possible occurrence of a common atmospheric state over Antarctica that includes a rather stable atmosphere inhibiting turbulent mixing, and a high riming efficiency driven by large cloud droplets. We then focus on a peculiar case study featuring a persistent layer with a particularly pronounced riming signature in triple-frequency radar data but only a relatively modest amount of supercooled liquid water. In-depth analysis of the radar observations suggests that such signatures can only be explained by the combined effects of moderately rimed aggregates or similarly shaped florid polycrystals and a narrow particle size distribution (PSD). Simulations of this case study performed with a one-dimensional bin model indicate that similar triple-frequency radar observations can be reproduced when narrow PSDs are simulated. Such narrow PSDs can in turn be explained by two key factors: (i) the presence of a shallow homogeneous droplet or humidified aerosol freezing layer aloft seeding an underlying supercooled liquid layer, and (ii) the absence of turbulent mixing throughout a stable polar atmosphere that sustains narrow PSDs, as hydrometeors grow from the nucleation region aloft to ice particles of several millimeters in size, by vapor deposition and then riming.

54 ENVIRONMENTAL SCIENCES↗

Impact of size and thermal gradient on supercooling of phase change materials for thermal energy storage

Phase change material based thermal energy storage has many current and potential applications in the heating and cooling of buildings, battery and electronics thermal management, thermal textiles, and dry cooling of power plants. However, connecting lab scale thermal data obtained with differential scanning calorimetry (DSC) to the performance of large-scale practical systems has been a major challenge primarily due to the dependence of supercooling on the size and temperature gradient of the system. Here we show how a phase change material’s supercooling behavior can be characterized experimentally using common lab scale thermal analysis techniques. We then develop a statistics based theoretical model that uses the lab-scale data on small samples to quantitatively predict the supercooling performance for a general thermal energy storage application of any size, including also allowing for the possibility of temperature gradients. Finally, we validate the modeling methodology by comparing to experimental results for solid-solid phase change in neopentyl glycol, which shows how the model successfully predicts the changes in supercooling temperature across a large range of cooling rates (2 orders of magnitude) and volumes (3 orders of magnitude). By accounting for thermal gradients, the model avoids ~2x error incurred by lumped approximations.

36 MATERIALS SCIENCE↗

Topology induced crossover between Langevin, subdiffusion, and Brownian diffusion regimes in supercooled water

Despite extensive studies of supercooled water, it remains challenging to understand its peculiar dynamic anomalous properties. In this work, we integrated full atomistic simulations of supercooled water over the temperature range of room temperature to 200 K using a quantum-mechanics-based polarizable force field with the dressed dynamics method that couples fast collision events and slow reorganization dynamics of hydrogen-bond networks. Our analysis unveils the salient multiscale features in the transient relaxation dynamics of supercooled water. A classical Langevin behavior dominates at fast timescales, while long-time relaxations unveil two different activation barriers in two temperature regions: below and above 230 K. The modulation of the entropy spectrum by temperature is elucidated in terms of a three-state model underlined by the complexity of the water dynamics associated with a topological transition of a strong hydrogen-bond network. This state-dependent network topology is quantitatively characterized by power-law exponents of inverse network connectivity from 200 to 298 K. Finally, this work provides valuable guidance for further studies on the transient relaxation dynamics of supercooled water.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Inherent-state melting and the onset of glassy dynamics in two-dimensional supercooled liquids

Below the onset temperature T o , the equilibrium relaxation time of most glass-forming liquids exhibits glassy dynamics characterized by a super-Arrhenius temperature dependence. In this supercooled regime, the relaxation dynamics also proceeds through localized elastic excitations corresponding to hopping events between inherent states, i.e., potential-energy-minimizing configurations of the liquid. Despite its importance in distinguishing the supercooled regime from the high-temperature regime, the microscopic origin of T o is not yet known. Here, we construct a theory for the onset temperature in two dimensions and find that an inherent-state melting transition, described by the binding–unbinding transition of dipolar elastic excitations, delineates the supercooled regime from the high-temperature regime. The corresponding melting transition temperature is in good agreement with the onset temperature found in various two-dimensional (2D) atomistic models of glass formers and an experimental binary colloidal system confined to a water–air interface. Additionally, we find the predictions for the renormalized elastic moduli to agree with the experimentally observed values for the latter 2D colloidal system. We further discuss the predictions of our theory on the displacement and density correlations at supercooled conditions, which are consistent with observations of the Mermin–Wagner fluctuations in experiments and molecular simulations.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ice-slurry production for solar-ice systems using supercooling with an in-stream crystallizer

Using ice slurry produced from supercooled water with an in-stream crystallizer opens a new path for solarice systems, increasing efficiency and reducing investment cost compared to ice-on-coil systems. Power needs are decoupled from the stored energy since the heat exchangers are not evenly distributed in the ice storage vessel but directly placed as the heat pump evaporator, which depends on the heat pump capacity and not on the ice storage volume. The novel ice storage design can serve as a heat source for a heat pump, where its evaporator is used to supercool water below 0 °C, or for refrigeration. The supercooled water at a temperature around −2 °C, maintained in a meta-stable liquid state, is triggered to nucleate in an in-stream crystallizer. The current design of the ice crystallizer allows for continuous operation of the system and scalability. Experimental results obtained with a gasketed plate heat exchanger used to supercool water and an in-stream crystallizer operated at a power of up to 6.5 kW are presented.

Thamm, Ann-Katrin↗

Interpreting T-History Data on Supercooling and Phase Change Enthalpy of a Salt-Hydrogel Complex for Building Thermal Management

Phase change materials (PCMs) are promising materials for storing and discharging latent heat in buildings to regulate the thermal environment. Measurement of salt hydrate PCM thermal performance is often challenging because of supercooling and phase segregation. Though differential scanning calorimetry (DSC) has been widely used to measure thermal properties of various phase change materials, DSC uses milligrams of sample and is unrealistic for predicting large-scale materials performance. The T-history method [1], in contrast, handles higher volumes but the analysis typically requires a lumped capacitance assumption. Here, we report and analyze T-History data on a novel salt-hydrogel complex with high viscosity, that renders low Biot number sample preparation extremely challenging. We re-examine the standard T-history method and compared against DSC data in this complex material. We report details of an experimental setup, built with necessary additions to a controlled environmental chamber. We carefully examine the validity of the lumped capacitance assumption and suggest a modified analysis using a computational approach for reliable data. Experimental parameters such as ramp rate and temperature range of the environmental chamber are considered via computational modeling to understand the effect of ramp rate on supercooling [2]. Finally, we report thermal cycling experiments on the salt-hydrogel complex. Our modified approach to measuring supercooling and enthalpy of fusion at large scales is important in better understanding the performance of phase-change materials at scale for building thermal storage. References: [1] Marin, Jose M, Belen Zalba, Luisa F Cabeza, and Harald Mehling. “Determination of Enthalpy Temperature Curves of Phase Change Materials with the Temperature-History Method: Improvement to Temperature Dependent Properties.” Measurement Science and Technology 14, no. 2 (February 1, 2003): 184–89. https://doi.org/10.1088/0957-0233/14/2/305. [2] Safari, A., R. Saidur, F.A. Sulaiman, Yan Xu, and Joe Dong. “A Review on Supercooling of Phase Change Materials in Thermal Energy Storage Systems.” Renewable and Sustainable Energy Reviews 70 (April 2017): 905–19. https://doi.org/10.1016/j.rser.2016.11.272

thermodynamics↗

Impact of Cooling Rate and Thermal Mass on Supercooling in a Salt-Hydrogel Complex for Thermal Energy Storage

Glauber’s salt is a promising phase change material for building thermal management because of its high latent heat, acceptable melting temperature of 32.3 °C for indoor air1,2. Despite these advantages, the practical application of Glauber’s salt in thermal energy storage systems is still challenging due to supercooling and phase segregation1–3. Here, we report the impact of temperature ramp rate and thermal mass on the supercooling of Glauber’s salt through the DSC and T-history experiment. The ramp rate effect was studied with a wide range of ramp rates in 1 to 10 °C/min in DSC and 1 to 4 °C/min in the T-history experiment. The thermal mass effect was investigated by comparing DSC and T-history experiment. The latent heat was also analyzed for different ramp rates and thermal mass conditions. The melting temperatures of Glauber’s salt from the two techniques were identical while freezing temperatures were different because of the thermal mass effect. During freezing in the T-history experiment, the latent heat was reduced by around 75% to the latent heat in melting due to supercooling and phase segregation. To overcome this bottleneck, we developed a novel hydrogel complex that reduces the supercooling and prevents phase segregation to maintain volumetric energy density for 100 cycles. Thermodynamic analysis accounting for composition shows that a higher salt composition can further enhance the volumetric energy storage density. For example, a 10% increase in the weight percentage of salt leads to about 50% enhancement in volumetric energy storage density. References: 1. D. R. Biswas, Solar Energy. 19, 99–100 (1977). 2. S. M. Hasnain, Energy Conversion and Management. 39, 1127–1138 (1998). 3. Byung Chul Shin, Sang Done Kim, P. Won-Hoon, Energy. 14, 921–930 (1989).

inorganic, thermodynamics↗

Supercooled Liquid Water Detection Capabilities from Ka-Band Doppler Profiling Radars: Moment-Based Algorithm Formulation and Assessment

The occurrence of supercooled liquid water in mixed-phase cloud (MPC) affects their cloud microphysical and radiative properties. The prevalence of MPCs in the mid- and high latitudes translates these effects to significant contributions to Earth’s radiative balance and hydrological cycle. The current study develops and assesses a radar-only, moment-based phase partition technique for the demarcation of supercooled liquid water volumes in arctic, MPC conditions. The study utilizes observations from the Ka band profiling radar, the collocated high spectral resolution lidar, and ambient temperature profiles from radio sounding deployments following a statistical analysis of 5.5 years of data (January 2014–May 2019) from the Atmospheric Radiation Measurement observatory at the North Slope of Alaska. The ice/liquid phase partition occurs via a per-pixel, neighborhood-dependent algorithm based on the premise that the partitioning can be deduced by examining the mean values of locally sampled probability distributions of radar-based observables and then compare those against the means of climatologically derived, per-phase probability distributions. Analyzed radar observables include linear depolarization ratio (LDR), spectral width, and vertical gradients of reflectivity factor and radial velocity corrected for vertical air motion. Results highlight that the optimal supercooled liquid water detection skill levels are realized for the radar variable combination of spectral width and reflectivity vertical gradient, suggesting that radar-based polarimetry, in the absence of full LDR spectra, is not as critical as Doppler capabilities. The cloud phase masking technique is proven particularly reliable when applied to cloud tops with an Equitable Threat Score (ETS) of 65%; the detection of embedded supercooled layers remains much more uncertain (ETS = 27%).

54 ENVIRONMENTAL SCIENCES↗

Partition between supercooled liquid droplets and ice crystals in mixed-phase clouds based on airborne in situ observations

Abstract. The onset of ice nucleation in mixed-phase clouds determines the lifetime and microphysical properties of ice clouds. In this work, we develop a novel method that differentiates between various phases of mixed-phase clouds, such as clouds dominated by pure liquid or pure ice segments, compared with those having ice crystals surrounded by supercooled liquid water droplets or vice versa. Using this method, we examine the relationship between the macrophysical and microphysical properties of Southern Ocean mixed-phase clouds at −40 to 0 °C (e.g. stratiform and cumuliform clouds) based on the in situ aircraft-based observations during the US National Science Foundation Southern Ocean Clouds, Radiation, Aerosol Transport Experimental Study (SOCRATES) flight campaign. The results show that the exchange between supercooled liquid water and ice crystals from a macrophysical perspective, represented by the increasing spatial ratio of regions containing ice crystals relative to the total in-cloud region (defined as ice spatial ratio), is positively correlated with the phase exchange from a microphysical perspective, represented by the increasing ice water content (IWC), decreasing liquid water content (LWC), increasing ice mass fraction, and increasing ice particle number fraction (IPNF). The mass exchange between liquid and ice becomes more significant during phase 3 when pure ice cloud regions (ICRs) start to appear. Occurrence frequencies of cloud thermodynamic phases show a significant phase change from liquid to ice at a similar temperature (i.e. −17.5 °C) among three types of definitions of mixed-phase clouds based on ice spatial ratio, ice mass fraction, or IPNF. Aerosol indirect effects are quantified for different phases using number concentrations of aerosols greater than 100 or 500 nm (N>100 and N>500, respectively). N>500 shows stronger positive correlations with ice spatial ratios compared with N>100. This result indicates that larger aerosols potentially contain ice-nucleating particles (INPs), which facilitate the formation of ice crystals in mixed-phase clouds. The impact of N>500 is also more significant in phase 2 when ice crystals just start to appear in the mixed phase compared with phase 3 when pure ICRs have formed, possibly due to the competing aerosol indirect effects on primary and secondary ice production in phase 3. The thermodynamic and dynamic conditions are quantified for each phase. The results show stronger in-cloud turbulence and higher updraughts in phases 2 and 3 when liquid and ice coexist compared with pure liquid or ice (phases 1 and 4, respectively). The highest updraughts and turbulence are seen in phase 3 when supercooled liquid droplets are surrounded by ice crystals. These results indicate both updraughts and turbulence support the maintenance of supercooled liquid water amongst ice crystals. Overall, these results illustrate the varying effects of aerosols, thermodynamics, and dynamics through various stages of mixed-phase cloud evolution based on this new method that categorizes cloud phases.

54 ENVIRONMENTAL SCIENCES↗

An anomalous structure disordering in Zr–Cu–Ag supercooled glass-forming liquids

An anomalous ordering-to-disordering transition in a Zr–Cu–Ag supercooled glass-forming liquid has been revealed by in situ high-energy x-ray diffraction. Upon heating, the supercooled liquid exhibits a structural crossover at T c = 716 K, evident by the change in statistical characteristics of the first sharp diffraction peak. When annealed in the vicinity of T c , the supercooled liquid first relaxes from its initial state to a denser and more ordered state. Subsequently, it becomes disordered at the medium-range scale with a slowing down of densification, as demonstrated by the broadening of the first sharp diffraction peak and a decrease in the peak intensities of the higher atomic shells in the reduced pair distribution function. Finally, a scenario for the evolution of less correlated locally favored clusters in the liquid–liquid phase transition is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observational constraint on a feedback from supercooled clouds reduces projected warming uncertainty

The increase of carbon-dioxide-doubling-induced warming (climate sensitivity) in the latest climate models is primarily attributed to a larger extratropical cloud feedback. This is thought to be partly driven by a greater ratio of supercooled liquid-phase clouds to all clouds, termed liquid phase ratio. We use an instrument simulator approach to show that this ratio has increased in the latest climate models and is overestimated rather than underestimated as previously thought. In our analysis of multiple models, a greater ratio corresponds to stronger negative cloud feedback, in contradiction with single-model-based studies. We trace this unexpected result to a cloud feedback involving a shift from supercooled to warm clouds as climate warms, which corresponds to greater cloud amount and optical depth and weakens the extratropical cloud feedback. Better constraining this ratio in climate models – and thus this supercooled cloud feedback – impacts their climate sensitivities by up to 1 °C and reduces inter-model spread.

54 ENVIRONMENTAL SCIENCES↗