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At least 991 records · Page 55

Synthesis of cuboid BiOCl nanosheets coupled with CdS quantum dots by region-selective deposition process with enhanced photocatalytic activity

Highlights: • Region-selective deposition process was adopted to prepare high-dispersed CdS QDs/BiOCl nanocomposites consisting of cuboid BiOCl nanosheets exposing (001) facet and CdS QDs with size of 5–10 nm. • The TGA was used as bridge linked the CdS QDs and BiOCl, which enables CdS QDs spread homogeneously on the (001) facet of BiOCl. • The optical absorption properties and charge transfer efficiency of CdS QDs/BiOCl nanocomposites are much improved owing to the widespread heterojunction between CdS QDs and BiOCl. • The photocatalytic degradation activities of CdS QDs/BiOCl composites are excellent for MO dyes and phenol contaminants under simulated solar and UV light, respectively. - Abstract: A facile region-selective deposition process was adopted to prepare high-dispersed CdS QDs on BiOCl nanosheets with the surface modification of thioglycollic acid (TGA). The samples were systematically characterized by XRD, SEM, TEM, HRTEM, EDS, XPS, UV–vis DRS, EIS and PL. The results indicate that CdS QDs with size of 5–10 nm dispersed uniformly on the surface of cuboid BiOCl nanosheets. The photocatalytic performance tests reveal that the CdS QDs-3%/BiOCl composite exhibits an excellent photocatalytic activity, which is over 4.0 and 4.8 times as high as pure BiOCl for methyl orange (MO) and phenol photodegradation rate under simulated solar light and UV light illumination, respectively. The enhanced photocatalytic performance of the CdS QDs/BiOCl composites should be attributed to the improved visible light absorption and the high migration efficiency of the photogenerated electron-holes due to the matched band gap and the widespread heterostructure between CdS QDs and BiOCl.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Magma intrusion near Volcan Tancitaro: Evidence from seismic analysis

Between May and June 2006, an earthquake swarm occurred near Volcan Tancítaro in Mexico, which was recorded by a temporary seismic deployment known as the MARS network. We located ~1000 events from this seismic swarm. Previous earthquake swarms in the area were reported in the years 1997, 1999 and 2000. We relocate and analyze the evolution and properties of the 2006 earthquake swarm, employing a waveform cross-correlation-based phase repicking technique. Hypocenters from 911 events were located and divided into eighteen families having a correlation coefficient at or above 0.75. 90% of the earthquakes provide at least sixteen phase picks. We used the single-event location code Hypo71 and the P-wave velocity model used by the Jalisco Seismic and Accelerometer Network to improve hypocenters based on the correlation-adjusted phase arrival times. We relocated 121 earthquakes, which show clearly two clusters, between 9–10 km and 3–4 km depth respectively. The average location error estimates are <1 km epicentrally, and <2 km in depth, for the largest event in each cluster. Depths of seismicity migrate upward from 16 to 3.5 km and exhibit a NE-SW trend. The swarm first migrated toward Paricutin Volcano but by mid-June began propagating back toward Volcán Tancítaro. In addition to its persistence, noteworthy aspects of this swarm include a quasi-exponential increase in the rate of activity within the first 15 days; a b-value of 1.47; a jug-shaped hypocenter distribution; a shoaling rate of ~5 km/month within the deeper cluster, and a composite focal mechanism solution indicating largely reverse faulting. As a result, these features of the swarm suggest a magmatic source elevating the crustal strain beneath Volcan Tancítaro.

58 GEOSCIENCES↗

High-Energy Charge-Separated States by Reductive Electron Transfer Followed by Electron Shift in the Tetraphenylethylene–Aluminum(III) Porphyrin–Fullerene Triad

A high-potential supramolecular triad (TPE-AlPor ← Im-C 60 ) composed of aluminum(III) porphyrin (AlPor), fullerene (C 60 ), and tetraphenylethylene (TPE) has been constructed. The fullerene and tetraphenylethylene units are bound axially to opposite faces of the porphyrin plane via coordination and covalent bonds, respectively. The ground and excited-state properties of the triad and reference dyads are studied using steady-state and time-resolved spectroscopic techniques. The transient data show that photoexcitation results in charge separation from tetraphenylethylene to the excited singlet state of the porphyrin ( 1 AlPor*), generating a high-energy (2.14 eV) charge-separated state, (TPE) •+ -(AlPor) •– , in toluene. A subsequent electron migration from the AlPor –• to fullerene generates a second high-energy (1.78 eV) charge-separated state (TPE) •+ -AlPor ← Im-(C60) •– . The lifetime of the charge separation is about 25 ns. Here, the high energy stored in the form of charge-separated states along with their reasonable lifetimes makes these donor–acceptor systems potential electron-transporting catalysts to carry out energy-demanding photochemical reactions, especially in artificial photosynthesis for conversion of solar energy into chemical energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular Interaction Regulates the Performance and Longevity of Defect Passivation for Metal Halide Perovskite Solar Cells

Defect passivation constitutes one of the most commonly used strategies to fabricate highly efficient perovskite solar cells (PSCs). However, the durability of the passivation effects under harsh operational conditions has not been extensively studied regardless of the weak and vulnerable secondary bonding between the molecular passivation agents and perovskite crystals. Here, we incorporated strategically designed passivating agents to investigate the effect of their interaction energies on the perovskite crystals and correlated these with the performance and longevity of the passivation effects. We unraveled that the passivation agents with a stronger interaction energy are advantageous not only for effective defect passivation but also to suppress defect migration. The prototypical PSCs treated with the optimal passivation agent exhibited superior performance and operational stability, retaining 81.9 and 85.3% of their initial performance under continuous illumination or nitrogen at 85 °C after 1008 h, respectively, while the reference device completely degraded during that time. Furthermore, this work provides important insights into designing operationally durable defect passivation agents for perovskite optoelectronic devices.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

H2 roaming chemistry and the formation of H3+ from organic molecules in strong laser fields

Roaming mechanisms, involving the brief generation of a neutral atom or molecule that stays in the vicinity before reacting with the remaining atoms of the precursor, are providing valuable insights into previously unexplained chemical reactions. Here in this paper, the mechanistic details and femtosecond time-resolved dynamics of H 3 + formation from a series of alcohols with varying primary carbon chain lengths are obtained through a combination of strong-field laser excitation studies and ab initio molecular dynamics calculations. For small alcohols, four distinct pathways involving hydrogen migration and H 2 roaming prior to H 3 + formation are uncovered. Despite the increased number of hydrogens and possible combinations leading to H 3 + formation, the yield decreases as the carbon chain length increases. The fundamental mechanistic findings presented here explore the formation of H 3 +, the most important ion in interstellar chemistry, through H 2 roaming occurring in ionic species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling Chemical Evolution of Cement Seals

The prevention of the migration of fluids is a field of study with high demand in both the private industry as well as in government research and development. More particularly, the prevention of carbon dioxide (CO 2 ) migration or return to the atmosphere. This, in turn, causes measurably significant atmospheric climate change that results in immense damage to the environment. In this study, the interaction between 0.5 molar sodium chloride (NaCl) brine solution and a cement interface over extended periods of time is computationally investigated, as well as the interaction of a 33 millimolar CO 2 dissolved in the afore-mentioned brine solution for the same period of time. A 2-meter-long saturated brine solution reacted with an 800-meter-long cement block in PFLOTRAN, an open-source reactive flow transport software whose output was later visualized in ParaView, a separate, open-source, visualization software.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Virtual file system for PSDS

This is a case study. It deals with the use of a 'virtual file system' (VFS) for Boeing's UNIX-based Product Standards Data System (PSDS). One of the objectives of PSDS is to store digital standards documents. The file-storage requirements are that the files must be rapidly accessible, stored for long periods of time - as though they were paper, protected from disaster, and accumulative to about 80 billion characters (80 gigabytes). This volume of data will be approached in the first two years of the project's operation. The approach chosen is to install a hierarchical file migration system using optical disk cartridges. Files are migrated from high-performance media to lower performance optical media based on a least-frequency-used algorithm. The optical media are less expensive per character stored and are removable. Vital statistics about the removable optical disk cartridges are maintained in a database. The assembly of hardware and software acts as a single virtual file system transparent to the PSDS user. The files are copied to 'backup-and-recover' media whose vital statistics are also stored in the database. Seventeen months into operation, PSDS is storing 49 gigabytes. A number of operational and performance problems were overcome. Costs are under control. New and/or alternative uses for the VFS are being considered.

Runnels, Tyson D.↗

Technology Assessment of High Capacity Data Storage Systems: Can We Avoid a Data Survivability Crisis?

This technology assessment of long-term high capacity data storage systems identifies an emerging crisis of severe proportions related to preserving important historical data in science, healthcare, manufacturing, finance and other fields. For the last 50 years, the information revolution, which has engulfed all major institutions of modem society, centered itself on data-their collection, storage, retrieval, transmission, analysis and presentation. The transformation of long term historical data records into information concepts, according to Drucker, is the next stage in this revolution towards building the new information based scientific and business foundations. For this to occur, data survivability, reliability and evolvability of long term storage media and systems pose formidable technological challenges. Unlike the Y2K problem, where the clock is ticking and a crisis is set to go off at a specific time, large capacity data storage repositories face a crisis similar to the social security system in that the seriousness of the problem emerges after a decade or two. The essence of the storage crisis is as follows: since it could take a decade to migrate a peta-byte of data to a new media for preservation, and the life expectancy of the storage media itself is only a decade, then it may not be possible to complete the transfer before an irrecoverable data loss occurs. Over the last two decades, a number of anecdotal crises have occurred where vital scientific and business data were lost or would have been lost if not for major expenditures of resources and funds to save this data, much like what is happening today to solve the Y2K problem. A pr-ime example was the joint NASA/NSF/NOAA effort to rescue eight years worth of TOVS/AVHRR data from an obsolete system, which otherwise would have not resulted in the valuable 20-year long satellite record of global warming. Current storage systems solutions to long-term data survivability rest on scalable architectures having parallel paths for data migration.

Halem, M.↗

Climate-Induced Boreal Forest Change: Predictions versus Current Observations

For about three decades, there have been many predictions of the potential ecological response in boreal regions to the currently warmer conditions. In essence, a widespread, naturally occurring experiment has been conducted over time. In this paper, we describe previously modeled predictions of ecological change in boreal Alaska, Canada and Russia, and then we investigate potential evidence of current climate-induced change. For instance, ecological models have suggested that warming will induce the northern and upslope migration of the treeline and an alteration in the current mosaic structure of boreal forests. We present evidence of the migration of keystone ecosystems in the upland and lowland treeline of mountainous regions across southern Siberia. Ecological models have also predicted a moisture-stress-related dieback in white spruce trees in Alaska, and current investigations show that as temperatures increase, white spruce tree growth is declining. Additionally, it was suggested that increases in infestation and wildfire disturbance would be catalysts that precipitate the alteration of the current mosaic forest composition. In Siberia, five of the last seven years have resulted in extreme fire seasons, and extreme fire years have also been more frequent in both Alaska and Canada. In addition, Alaska has experienced extreme and geographically expansive multi-year outbreaks of the spruce beetle, which had been previously limited by the cold, moist environment. We suggest that there is substantial evidence throughout the circumboreal region to conclude that the biosphere within the boreal terrestrial environment has already responded to the transient effects of climate change. Additionally, temperature increases and warming-induced change are progressing faster than had been predicted in some regions, suggesting a potential non-linear rapid response to changes in climate, as opposed to the predicted slow linear response to climate change.

Soja, Amber J.↗

Candidate Electromagnetic Counterpart to the Binary Black Hole Merger Gravitational-Wave Event S190521g

We report the first plausible optical electromagnetic counterpart to a (candidate) binary black hole merger. Detected by the Zwicky Transient Facility, the electromagnetic flare is consistent with expectations for a kicked binary black hole merger in the accretion disk of an active galactic nucleus [B. McKernan, K. E. S. Ford, I. Bartoset al., Astrophys. J. Lett.884, L50 (2019)] and is unlikely [<O(0.01%))] due to intrinsic variability of this source. The lack of color evolution implies that it is not a supernova and instead is strongly suggestive of a constant temperature shock. Other false-positive events, such as microlensing ora tidal disruption event, are ruled out or constrained to be <O(0.1%). If the flare is associated withS190521g, we find plausible values of total mass M(BBH) ∼ 100 Mꙩ, kick velocity v(k) ∼ 200 km/s at θ ∼ 60° in a disk with aspect ratio H/a ∼ 0.01(i.e., disk height H at radius a) and gas density ρ ∼ 10^(−10)g/cu.cm. The merger could have occurred at a disk migration trap (a ∼ 700 r(g); r(g) ≡ GM(SMBH)/sq.c, where M(SMBH) is the mass of the active galactic nucleus supermassive black hole). The combination of parameters implies a significant spin for at least one of the black holes in S190521g. The timing of our spectroscopy prevents useful constraints on broad-line asymmetry due to an off-center flare. We predict a repeat flare in this source due to a reencountering with the disk in ∼ 1.6 yr(M(SMBH)/10^(8) Mꙩ)(a/10^(3)r(g))^(3/2).

M. J. Graham↗

Combustor-Turbine Interactions By Using the Open National Combustion Code (OpenNCC) and the Glenn-HT Code

We develop the methodology of coupling two different computational fluid dynamic (CFD) codes, OpenNCC and Glenn-HT, in order to investigate the unsteady flow fields inside the combustor and around the first-stage stator of a high-pressure turbine (HPT) from the energy efficient engine (E 3 ) program. In our coupling strategy, OpenNCC, a time accurate unstructured mesh multi-phase combustion CFD code, is applied to the combustor region and Glenn-HT, a structured mesh CFD code designed for turbine applications, is utilized inside the HPT region. As a proof of concept, we first simulate the three-dimensional airflow over the backward facing step and compared the predicted pressure coefficient against experimental data. We then considered a Jet-A/Air combustor with the NASA single learn direct injector (LDI) as a reacting flow test case. Here, Glenn-HT is used in the downstream of the combustor and assumes that the working fluid is a single gas (i.e., air) where the properties of the gas are taken from time- and area-averaged values at the combustor exit. A fully coupled combustor-turbine simulation using both OpenNCC and Glenn-HT was conducted on the E 3 combustor and a detailed analysis done pertaining to how a realistic combustor outflow affects migration of hot-streaks and its impact on the aerodynamic behavior inside the HPT. It is found that the combustion dynamics (i.e., the switching main and pilot flame strength) significantly alters the aerodynamic behavior inside the HPT including hot-streak migration. Variations of the temperature and the velocity magnitude in the passage could be up to ±75 and ±15. These large variations are an important part of the combustor-turbine interactions, which are overlooked by a single component simulation of the HPT while imposing the steady inflow boundary condition at the HPT inlet. Finally, it is observed the strong density gradient associated with the hot-streaks and the pressure gradient at the passage significantly enhances the baroclinic torque, affecting the vorticity field.

CFD hot-streaks↗

Electron dynamics in complex environments with real-time time dependent density functional theory in a QM-MM framework

This article presents a time dependent density functional theory (TDDFT) implementation to propagate the Kohn-Sham equations in real time, including the effects of a molecular environment through a Quantum-Mechanics Molecular-Mechanics (QM-MM) hamiltonian. The code delivers an all-electron description employing Gaussian basis functions, and incorporates the Amber force-field in the QM-MM treatment. The most expensive parts of the computation, comprising the commutators between the hamiltonian and the density matrix—required to propagate the electron dynamics—, and the evaluation of the exchange-correlation energy, were migrated to the CUDA platform to run on graphics processing units, which remarkably accelerates the performance of the code. The method was validated by reproducing linear-response TDDFT results for the absorption spectra of several molecular species. Two different schemes were tested to propagate the quantum dynamics: (i) a leap-frog Verlet algorithm, and (ii) the Magnus expansion to first-order. These two approaches were confronted, to find that the Magnus scheme is more efficient by a factor of six in small molecules. Interestingly, the presence of iron was found to seriously limitate the length of the integration time step, due to the high frequencies associated with the core-electrons. This highlights the importance of pseudopotentials to alleviate the cost of the propagation of the inner states when heavy nuclei are present. Finally, the methodology was applied to investigate the shifts induced by the chemical environment on the most intense UV absorption bands of two model systems of general relevance: the formamide molecule in water solution, and the carboxy-heme group in Flavohemoglobin. In both cases, shifts of several nanometers are observed, consistently with the available experimental data.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Striped Mullet Migration Patterns in the Indian River Lagoon: A Network Analysis Approach to Spatial Fisheries Management

Striped mullet (Mugil cephalus) are numerically abundant forage fish, highly valuable as prey and commercially valuable to humans. From September to December, mullet in the Indian River Lagoon (IRL), Florida undergo an annual migration from inshore foraging habitats to oceanic spawning sites. However, their migratory pathways, in particular their intra-estuarine movement pathways, remain unknown. To address this knowledge gap, we utilized passive acoustic telemetry to assess the movement patterns of M. cephalus within the IRL. Thirty-two fish were tagged, generating usable tracks from 18 individuals. The mean (±s.d.) time that fish were detected in the array was ~38 ± 90 days, with the longest at 444 days. We also document the first evidence of skipped spawning in M. cephalus inhabiting waters of the southeastern United States. These data suggest impoundments around the Merritt Island National Wildlife Refuge appear to serve as important refugia for striped mullet while the Banana and Indian Rivers act as corridors during their inshore migratory movements. Through spatial fisheries management, high value habitat and connective elements utilized by mullet and other vital forage fish may be identified, to benefit both natural and human dynamics in estuarine systems.

Acoustic telemetry↗

One-Dimensional Reaction-Diffusion Simulation of Cu Migration in Polycrystalline CdTe Solar Cells

In this work, we report on developing 1D reaction-diffusion solver to understand the kinetics of p-type doping formation in CdTe absorbers and to shine some light on underlying causes of metastabilities observed in CdTe PV devices. Evolution of intrinsic and Cu-related defects in CdTe solar cell has been studied in time-space domain self-consistently with free carrier transport and Poisson equation. Resulting device performance was simulated as a function of Cu diffusion anneal time showing pronounced effect the evolution of associated acceptor and donor states can cause on device characteristics. Although 1D simulation has intrinsic limitations when applied to poly-crystalline films, the results suggest strong potential of the approach in better understanding of the performance and metastabilities of CdTe photovoltaic device.

14 SOLAR ENERGY↗

A Theoretical Study on Reaction Mechanisms and Kinetics of Thiophene Hydrodesulfurization over MoS 2 Catalysts

In the present work, thiophene hydrodesulphurization (HDS) over the Mo-edge, the S-edge, and the Mo-S connection edge of MoS 2 catalyst with 50% sulfur coverage was studied using first-principles based microkinetic modeling. Two parallel HDS routes, i.e., direct desulfurization (DDS) and hydrogenation (HYD) were taken into account. It has been found that the major reaction route of thiophene HDS on the Mo- and the Mo-S edges is temperature dependent. In the low temperature range of 500~600 K, the HYD route is dominant, leading to the C 4 H 8 formation. As the temperature increases, the DDS route becomes competitive with the HYD route. At the temperature above 650 K, the DDS route will be the dominant HDS reaction route on the Mo- and the Mo-S edges. While the DDS route that leads to the formation of C4H6 is the major thiophene HDS reaction route on the S-edge in the entire temperature range of 500~750 K. The microkinetic modeling results show the overall HDS activity on the S-edge is lower than it on the Mo- and the Mo-S edges. The Mo-S edge also provides a preferential reaction pathway, which facilitates 2-hydrothiophene migration from the Mo-edge to the S-edge, followed by remaining elementary steps with lower activation barriers in the DDS route. The work was financially supported by the National Natural Science Foundation of China (No. 21476012, 21571012, 21407007 and 91534201). The computing time was granted by a scientific theme user proposal in the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL), which is a U.S. Department of Energy national scientific user facility located at Pacific Northwest National Laboratory (PNNL) in Richland, Washington. Part of computing time was provided the National Energy Research Scientific Computing Center (NERSC). D. Mei is supported by the US Department of Energy, Office of Sciences, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences.

Thiophene, hydrodesulphurization, MoS2, DFT, micro↗

Hydroxyacetone production from C 3 Criegee intermediates

Hydroxyacetone (CH 3 C(O)CH 2 OH) is observed as a stable end product from reactions of the (CH 3 ) 2 COO Criegee intermediate, acetone oxide, in a flow tube coupled with multiplexed photoionization mass spectrometer detection. In the experiment, the isomers at m/z = 74 are distinguished by their different photoionization spectra and reaction times. Hydroxyacetone is observed as a persistent signal at longer reaction times at a higher photoionization threshold of ca. 9.7 eV than Criegee intermediate and definitively identified by comparison with the known photoionization spectrum. Complementary electronic structure calculations reveal multiple possible reaction pathways for hydroxyacetone formation, including unimolecular isomerization via hydrogen atom transfer and –OH group migration as well as self-reaction of Criegee intermediates. Varying the concentration of Criegee intermediates suggests contributions from both unimolecular and self-reaction pathways to hydroxyacetone. As a result, the hydroxyacetone end product can provide an effective, stable marker for the production of transient Criegee intermediates in future studies of alkene ozonolysis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ion-Assisted Ligand Exchange for Efficient and Stable Inverted FAPbI 3 Quantum Dot Solar Cells

Perovskite quantum dot (QD) has emerged as a promising material for photovoltaics with its superior stability compared to their three-dimensional bulk counterparts, owing to its thermodynamically stabilized photoactive phase. However, ligand management on perovskite QD surfaces is extremely difficult due to the ionic nature of the perovskite lattice, which often leads to either incomplete removal of the native insulating ligands or formation of trap states during the ligand-exchange process, greatly hampering the photovoltaic performances. In this work, we report an ion-assisted ligand-exchange method for FAPbI 3 QDs using AOAc (A = formamidinium (FA + ), guanidinium (GA + ), and phenethylammonium (PEA + ), OAc = acetate), with the A + and OAC - ions promoting the removal of native long-chain insulating ligands. Further, the more complete ligand exchange results in dense and well-oriented packing of QDs, together with the enhancement of electronic coupling and charge transport across QDs. In addition, the A + and OAC - ions can fill the surface A-/X-site vacancies, respectively, reducing the QD surface trap state density and hence suppressing charge recombination and iodide migration. The p-i-n inverted QD solar cells fabricated with this ligand-exchange method exhibit significant enhancement in shortcircuit current density (J SC ), reaching a PCE of 10.13%. Moreover, unencapsulated devices show impressive stabilities of more than 7300 h (10 months) storage time in a N 2 -filled glovebox.

36 MATERIALS SCIENCE↗

Interaction of the Westerlies with the Tibetan Plateau in Determining the Mei-Yu Termination

This article explores how the termination of the mei-yu is dynamically linked to the westerlies impinging on the Tibetan Plateau. It is found that the mei-yu stage terminates when the maximum upper-tropospheric westerlies shift beyond the northern edge of the plateau, around 40°N. This termination is accompanied by the disappearance of tropospheric northerlies over northeastern China. The link between the transit of the jet axis across the northern edge of the plateau, the disappearance of northerlies, and termination of the mei-yu holds on a range of time scales from interannual through seasonal and pentad. Diagnostic analysis indicates that the weakening of the meridional moisture contrast and meridional wind convergence, mainly resulting from the disappearance of northerlies, causes the demise of the mei-yu front. The authors propose that the westerlies migrating north of the plateau and consequent weakening of the extratropical northerlies triggers the mei-yu termination. Model simulations are employed to test the causality between the jet and the orographic downstream northerlies by repositioning the northern edge of the plateau. As the plateau edge extends northward, orographic forcing on the westerlies strengthens, leading to persistent strong downstream northerlies and a prolonged mei-yu. Idealized simulations with a dry dynamical core further demonstrate the dynamical link between the weakening of orographically forced downstream northerlies with the positioning of the jet from south to north of the plateau. Changes in the magnitude of orographically forced stationary waves are proposed to explain why the downstream northerlies disappear when the jet axis migrates beyond the northern edge of the plateau.

54 ENVIRONMENTAL SCIENCES↗