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At least 19 records

A Time-Gated, Time-Correlated Single-Photon-Counting Lidar to Observe Atmospheric Clouds at Submeter Resolution

Most lidars used for cloud observations have the range resolution of about 10 m, so they are incapable of resolving submeter-scale processes that are crucial to cloud evolution. This article describes a prototype of a ground-based, vertically pointing, time-gated, time-correlated single-photon-counting lidar (referred to as the T2 lidar) developed to explore atmospheric clouds at range resolution two orders of magnitude finer than traditional atmospheric lidars. The T2 lidar emits green-light pulses (532 nm) at a repetition rate of 20.6 kHz and a pulse width of ∼650 ps, which enables the observation of aerosol and cloud layers at heights from a few hundred meters to 7.28 km above the ground level at range resolution down to 10 cm. In addition, a digital delay pulse generator controls the detector to only receive photons for a short period after each laser pulse. This time-gated technique blocks photons arriving from regions outside the target zone, thus significantly reducing the noise level and allowing observation even inside clouds. Initial observations show that the T2 lidar can detect sharp cloud boundaries and fine structures near the cloud base. Such refined measurements of cloud structure could lead to an improved understanding of microphysical processes such as droplet activation, entrainment and mixing, and precipitation.

54 ENVIRONMENTAL SCIENCES↗

Xanthophyll-cycle based model of the rapid photoprotection of Nannochloropsis in response to regular and irregular light/dark sequences

We explore the photoprotection dynamics of Nannochloropsis oceanica using time-correlated single photon counting under regular and irregular actinic light sequences. The varying light sequences mimic natural conditions, allowing us to probe the real-time response of non-photochemical quenching (NPQ) pathways. Durations of fluctuating light exposure during a fixed total experimental time and prior light exposure of the algae are both found to have a profound effect on NPQ. These observations are rationalized with a quantitative model based on the xanthophyll cycle and the protonation of LHCX1. The model is able to accurately describe the dynamics of non-photochemical quenching across a variety of light sequences. The combined model and observations suggest that the accumulation of a quenching complex, likely zeaxanthin bound to a protonated LHCX1, is responsible for the gradual rise in NPQ. Additionally, the model makes specific predictions for the light sequence dependence of xanthophyll concentrations that are in reasonable agreement with independent chromatography measurements taken during a specific light/dark sequence.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of 6 Li-loaded pulse-shape-discriminating plastic scintillators

Lithium-loaded organic plastic scintillators combine sensitivity to γ rays with the ability to detect both fast and slow neutrons, making them valuable for applications in nuclear security and in basic nuclear and particle physics. The goal of this work is to characterize the neutron response of two custom lithium-loaded organic plastic scintillators developed at Lawrence Livermore National Laboratory. Both are ternary polystyrene-based formulations containing 1.5 wt.% 6 Li salts of isobutyric acid, but they differ in their primary and secondary dye compositions: one uses m-terphenyl as the primary fluor and with Exalite 404 as the wavelength shifter, whereas the other uses 2,5-diphenyloxazole (PPO) and 9,10-diphenyl-anthracene, respectively. The temporal response of the scintillators was measured via time-correlated single photon counting for γ-ray and neutron events. The proton light yield was measured using the double time-of-flight technique from 1.3 to 15 MeV at the 88-Inch Cyclotron at Lawrence Berkeley National Laboratory. For the slow neutron response, an AmBe source moderated with polyethylene was used, and the light output from the 6 Li(n,α)t reaction was characterized. Differences in ionization quenching and temporal response were observed between the two materials with the PPO-containing scintillator exhibiting higher ionization quenching. These results provide performance benchmarks that can guide the design and optimization of future lithium-loaded plastic scintillators for use in basic science and applications.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Preferential Direction of Electron Transfers at a Dye–Metal Oxide Interface with an Insulating Fluorinated Self-Assembled Monolayer and MgO

Slowing non-desirable electron transfer reactions at metal oxide-dye interfaces is important for many technologies. Specifically, after an interfacial photoinduced charge separation event at a metal oxide-dye interface, it is critically important to limit the rate of electron transfer reactions back to sensitizers and to limit electron transfer reactions between the electrolyte and the metal oxide. Ruthenium-based dyes at metal oxide interfaces are widely used in many fields; however, these dyes often have poor surface insulation resulting in fast recombination kinetics with transition metal-based redox shuttles in an electrolyte. This work explores two semiconductor surface modification strategies designed to minimize recombination events of electrons in TiO 2 with oxidized redox shuttles using a fluorinated siloxane insulator (PFTS) and a metal oxide insulator (MgO) with a well-known Ru dye, B11. Additionally, the influence of these treatments on the rate and duration of photoinduced interfacial charge separation at the TiO 2 -dye interface was examined. The TiO 2 -dye-redox shuttle systems were studied via dye-sensitized solar cell current-voltage curve, incident photon-to-current conversion efficiency, small-modulated photovoltage transient, time-correlated single photon counting, and transient absorption spectroscopy measurements. MgO was found to decrease the rate of the electron transfer reaction from the metal oxide to the electrolyte, decrease the rate of the electron transfer reaction to the oxidized dye from TiO 2 , increase the electron transfer reaction rate from a reduced redox shuttle to an oxidized dye, and decrease the electron injection rate from the photoexcited dye to TiO2. Interestingly, PFTS was found to desirably improve on these rates relative to MgO or untreated TiO 2 . Here, a model based on electrostatic interactions is presented to explain the exceptional behavior of PFTS with DFT computational analysis of PFTS supporting this model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Investigating the Role π -Rich Solvents Play in the Growth of Cesium Lead Bromide Nanocrystals

In this report, the role that a high-boiling-point solvent type plays on the nucleation and growth, morphology, and crystal-phase transformation of cesium lead bromide nanocrystals (CsPbBr 3 ) is studied. The CsPbBr 3 products were compared between a one-pot growth mechanism at room temperature (RT) versus a hot-injection mechanism (HI) control using dibenzyl ether (DBE), diphenyl ether (DPE), dioctyl ether (DOE), or 1- octadecene (ODE). The coordination between these solvents and the PbBr 2 salt precursors resulted in different plumbate [PbSBr n ] 2−n precursors being formed. The S-to-Pb 2+ coordination within [PbSBr n ] 2−n was probed by UV−vis and solvent-phase 207 Pb NMR, both of which showed considerable coordination between [PbSBr n ] 2−n and the π-rich DBE and DPE, whose reactivity affected CsPbBr 3 growth. The effect was more pronounced for CsPbBr 3 prepared via RT, where the morphology was tunable, with π-rich solvents producing thin rod-like CsPbB r3 with a blue emission, compared to the green-emitting thicker platelets formed via HI. While XRD showed crystalline products for both RT and HI, with orthorhombic and cubic forms, respectively, the RT products had considerable surface defects, as was indicated by lower quantum yields, and to understand this the photoluminescent lifetimes were measured by time-correlated single photon counting.

207Pb NMR↗

Correlating Broadband Photoluminescence with Structural Dynamics in Layered Hybrid Halide Perovskites

The emission of white light from a single material is atypical and is of interest for solid-state lighting applications. Broadband light emission has been observed in some layered perovskite derivatives, A 2 PbBr 4 (A = R-NH 3 + ), and correlates with static structural distortions corresponding to out-of-plane tilting of the lead bromide octahedra. While materials with different organic cations can yield distinct out-of-plane tilts, the underlying origin of the octahedral tilting remains poorly understood. Using high energy resolution (e.g., quasi-elastic) neutron scattering, this contribution details the rotational dynamics of the organic cations in A 2 PbBr 4 materials where A = n-butylammonium (nBA), 1,8-diaminooctammonium (ODA), and 4-aminobutyric acid (GABA). The organic cation dynamics differentiate (nBA) 2 PbBr 4 from (ODA)PbBr 4 or (GABA) 2 PbBr 4 in that the larger spatial extent of dynamics of nBA yields a larger effective cation radius. The larger effective volume of the nBA cation in (nBA) 2 PbBr 4 yields a closer to ideal A-site geometry, preventing the out-of-plane tilt and broadband luminescence. In all three compounds, we observe hydrogen dynamics attributed to rotation of the ammonium headgroup and at a time scale faster than the white light photoluminescence studied by time-correlated single photon counting spectroscopy. This supports a previous assignment of the broadband emission as resulting from a single ensemble, such that the emissive excited state experiences many local structures faster than the emissive decay. Furthermore, the findings presented here highlight the role of the organic cation and its dynamics in hybrid organic–inorganic perovskites and white light emission.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

High-Resolution LiDAR Observations for Coupled Effects of Dry-Air Entrainment and Haze-Cloud Interactions on Cloud Vertical Structure

This study demonstrates the high-resolution profiling of cloud microphysics in a laboratory chamber using Time-Correlated Single Photon Counting (TCSPC) LiDAR. We present a novel retrieval method to derive vertical extinction (𝜎) profiles, constrained by in situ measurements, to diagnose responses to dry-air entrainment. In clean clouds, the LiDAR signals and retrieved 𝜎 remain relatively uniform, with entrainment effects confined to the upper layer. In contrast, polluted clouds exhibit strong vertical variability and a transition to a water-vapor-limited state. Entrainment significantly enhances the haze number concentration (𝑁ℎ), particularly near the bottom, creating highly height-dependent extinction profiles for polluted clouds. Our results highlight the capability of high-resolution LiDAR in capturing fine-scale vertical inhomogeneities. This approach provides a robust framework for quantifying how aerosol loading modulates entrainment sensitivity, offering new insights into the transition between buffered and water-vapor-limited regimes.

54 ENVIRONMENTAL SCIENCES↗

Radiative dynamics and delayed emission in pure and doped InP/ZnSe/ZnS quantum dots

We have used time-correlated single photon counting to elucidate the radiative dynamics of InP/ZnSe/ZnS core/shell/shell quantum dots (QDs) that differ in the amount and distribution of excess indium. Stoichiometric QDs having an In:P atom ratio very near unity exhibit simple luminescence kinetics. The photoluminescence (PL) rises with the 40 ps instrument response function and exhibits a decay that is close to a single exponential with a time constant that decreases from 32 to 28 ns with increasing shell thickness. QDs having excess indium (In:P ratio of 1.15–1.63) show a significant component of a slower rise time assigned to transient population of indium-based hole traps in the ZnSe shell. They also have a slower PL decay, attributed to an equilibrium between these traps, which are optically dark, and the emissive valence-band state. This results in a radiative lifetime that increases from 32 to 48 ns with increasing shell thickness. Different treatments of the InP cores prior to shell deposition result in different core/shell interfaces as indicated by resonance Raman spectroscopy, as well as differences in the amplitude and timescale of the slow PL rise and the PL decay time. These are interpreted in terms of different radial distributions of the indium-based hole traps, which can be related to differences in the interfacial lattice strain.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Axial vs equatorial: Capturing the intramolecular charge transfer state geometry in conformational polymorphic crystals of a donor–bridge–acceptor dyad in nanosecond-time-scale

Two conformational polymorphs of a donor–bridge–acceptor (D-B-A) dyad, p-(CH 3 ) 2 N-C 6 H 4 -(CH 2 ) 2 -(1-pyrenyl)/PyCHDMA, were studied, where the electron donor (D) moiety p-(CH 3 ) 2 N-C 6 H 4 /DMA is connected through a bridging group (B), –CH 2 –CH 2 –, to the electron acceptor (A) moiety pyrene. Though molecular dyads like PyCHDMA have the potential to change solar energy into electrical current through the process of photoinduced intramolecular charge transfer (ICT), the major challenge is the real-time investigation of the photoinduced ICT process in crystals, necessary to design solid-state optoelectronic materials. The time-correlated single photon counting (TCSPC) measurements with the single crystals showed that the ICT state lifetime of the thermodynamic form, PyCHDMA1 (pyrene and DMA: axial), is ~3 ns, whereas, for the kinetic form, PyCHDMA20 (pyrene and DMA: equatorial), it is ~7 ns, while photoexcited with 375 nm radiation. The polymorphic crystals were photo-excited and subsequently probed with a pink Laue x-ray beam in time-resolved x-ray diffraction (TRXRD) measurements. The TRXRD results suggest that in the ICT state, due to electron transfer from the tertiary N-atom in DMA moiety to the bridging group and pyrene moiety, a decreased repulsion between the lone-pair and the bond-pair at N-atom induces planarity in the C–N–(CH 3 ) 2 moiety, in both polymorphs. The Natural Bond Orbital calculations and partial atomic charge analysis by Hirshfeld partitioning also corroborated the same. Although the interfragment charge transfer (IFCT) analysis using the TDDFT results showed that for the charge transfer excitation in both conformers, the electrons were transferred from the DMA moiety to mostly the pyrene moiety, the bridging group has little role to play in that.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Peering into cloud physics using ultra-fine resolution radar and lidar systems

Cloud microphysical processes, such as droplet activation, condensational growth, and collisional growth, play a central role in the evolution of clouds and precipitation. Accurate representations of these processes in numerical models are challenging partially due to incomplete understanding of them at the process-level arising from limited systematic observations. Most surface-based active remote sensors, including today’s operational cloud radars and lidars, have a resolution on the order of tens of meters. This resolution is insufficient to resolve cloud microphysical processes that manifest at finer (meter and sub-meter) scales. A new set of ultra-high-resolution ground-based radar and lidar systems have been developed to address this observational gap. The newly developed 94-GHz cloud radar has a range resolution down to 2.8 m, or a factor of 10 finer than typical radars, using a large bandwidth and quadratic phase coding techniques. The lidar has a range resolution down to 10 cm, or a factor of 100 finer than typical lidars, using a time-gated time-correlated single photon counting technique. Such high-resolution observations were previously only achievable through in situ aircraft measurements. Even then, aircraft measurements do not permit continuous long-term cloud observation as is possible with ground-based remote sensing instruments. In this study, the first-light cloud observations from the new radar and lidar systems are shown to reveal detailed cloud structures that conventional sensors could only perceive in a bulk sense, thus providing new avenues to investigate cloud microphysical processes and their impact on weather and climate.

54 ENVIRONMENTAL SCIENCES↗

3D, Real-time Label-free Visualization of Cellular Health

This work directly addresses a key question raised in TA7, Topic L1 of HDTRA1-16-24-FRCWMDCall, “Can quantum level changes be detected, mapped, and understood in the biological environment to allow faster diagnostic responses?” This work will use the inherently sensitive quantum property of a molecular excited state lifetime to visualize and map discrete, subtle nanometer-scale changes (e.g. NADPH vs NADH) that are key indicators of cellular health in response to chemical and biological threats and MCMs. It will also develop and exploit new, fast imaging light-sheet methods to allow faster diagnostic responses. This new imaging system will exploit time-correlated single photon counting and new advances in single-objective light-sheet microscopy (oblique plane microscopy) for fast, quantitative analysis of cellular redox state. We will add an entirely new dimension (excited state fluorescence lifetime) to oblique plane microscopy—a method that even without this added dimension was labeled by Nature Methods in 2021 as a ‘Method to Watch.’ Following instrument development and validation, we will explore cellular response to Burkholderia infections and antibiotic treatment in immortal cell lines followed by expansion to more realistic cellular environments (such as neuro-muscular junctions, NMJs) to test nerve agent simulants and their MCMs. As a microscopy platform, these methods hold the promise of being able to visualize a single infected cell (or a cellular compartment) and MCM treatment well before a larger and later organ/organism response.

47 OTHER INSTRUMENTATION↗

On the uncertainty in single molecule fluorescent lifetime and energy emission measurements

Time-correlated single photon counting has recently been combined with mode-locked picosecond pulsed excitation to measure the fluorescent lifetimes and energy emissions of single molecules in a flow stream. Maximum likelihood (ML) and least square methods agree and are optimal when the number of detected photons is large however, in single molecule fluorescence experiments the number of detected photons can be less than 20, 67% of those can be noise and the detection time is restricted to 10 nanoseconds. Under the assumption that the photon signal and background noise are two independent inhomogeneous poisson processes, we derive the exact joint arrival time probably density of the photons collected in a single counting experiment performed in the presence of background noise. The model obviates the need to bin experimental data for analysis, and makes it possible to analyze formally the effect of background noise on the photon detection experiment using both ML or Bayesian methods. For both methods we derive the joint and marginal probability densities of the fluorescent lifetime and fluorescent emission. the ML and Bayesian methods are compared in an analysis of simulated single molecule fluorescence experiments of Rhodamine 110 using different combinations of expected background nose and expected fluorescence emission. While both the ML or Bayesian procedures perform well for analyzing fluorescence emissions, the Bayesian methods provide more realistic measures of uncertainty in the fluorescent lifetimes. The Bayesian methods would be especially useful for measuring uncertainty in fluorescent lifetime estimates in current single molecule flow stream experiments where the expected fluorescence emission is low. Both the ML and Bayesian algorithms can be automated for applications in molecular biology.

Brown, Emery N.↗

On the Uncertainty in Single Molecule Fluorescent Lifetime and Energy Emission Measurements

Time-correlated single photon counting has recently been combined with mode-locked picosecond pulsed excitation to measure the fluorescent lifetimes and energy emissions of single molecules in a flow stream. Maximum likelihood (ML) and least squares methods agree and are optimal when the number of detected photons is large, however, in single molecule fluorescence experiments the number of detected photons can be less than 20, 67 percent of those can be noise, and the detection time is restricted to 10 nanoseconds. Under the assumption that the photon signal and background noise are two independent inhomogeneous Poisson processes, we derive the exact joint arrival time probability density of the photons collected in a single counting experiment performed in the presence of background noise. The model obviates the need to bin experimental data for analysis, and makes it possible to analyze formally the effect of background noise on the photon detection experiment using both ML or Bayesian methods. For both methods we derive the joint and marginal probability densities of the fluorescent lifetime and fluorescent emission. The ML and Bayesian methods are compared in an analysis of simulated single molecule fluorescence experiments of Rhodamine 110 using different combinations of expected background noise and expected fluorescence emission. While both the ML or Bayesian procedures perform well for analyzing fluorescence emissions, the Bayesian methods provide more realistic measures of uncertainty in the fluorescent lifetimes. The Bayesian methods would be especially useful for measuring uncertainty in fluorescent lifetime estimates in current single molecule flow stream experiments where the expected fluorescence emission is low. Both the ML and Bayesian algorithms can be automated for applications in molecular biology.

Brown, Emery N.↗

Generation of a fluorescent short-lifetime oxygen nanosensor by coupling of an exciplex forming dye pair

Typical oxygen-sensitive dyes have lifetimes in the μs-ms regime for sensitive oxygen detection based on molecular quenching. Due to the long triplet-state lifetimes and poor quenching efficiency of these probes, it has been difficult to develop short lifetime probes. We have developed oxygen sensors using a short-lifetime dye (∼30–60 ns) that forms an anthracene-aniline exciplex, which is quenched by molecular oxygen through an excited-state charge transfer mechanism. To achieve measurements in aqueous systems, we have tethered the dyes together via a C3 alkyl linker to facilitate greater exciplex formation at low dye concentration (20 μg mL −1 ) and encapsulated the resulting compound into polymeric nanoparticles to form an aqueous-dispersible short-lifetime oxygen nanosensor. The sensors emit at 420 nm (unfolded dye) and 500 nm (exciplex), and the ratiometric Stern-Volmer Constant is 1.52 ± 0.02 L mol −1 , showing good sensitivity from 0 % to 40 % dissolved oxygen without the tradeoff of a long lifetime needed for direct molecular quenching. In this paper, we characterize this sensor for both lifetime-based measurements using time-correlated single-photon counting and ratiometric intensity-based measurements using the unfolded dye emission as an internal reference peak.

Biological and medical sciences↗

Laser-Assisted Synthesis of Monolayer 2D MoSe 2 Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing

We report tuning the structural and electronic properties of atomically thin two-dimensional (2D) materials via defect and vacancy engineering is the key to enabling their potential use in various applications, including electronics, energy, and sensing devices. Vacancies are, for instance, becoming highly promising for the enhanced interaction of gases and biomolecules with 2D materials in energy and sensing applications. However, the deterministic generation of desirable vacancies with tunable concentrations remains a challenge in 2D materials due to the limitations in the current growth methods, such as the complex reaction chemistries and gas flow dynamics. Therefore, engineering defects and vacancies in 2D materials have been mainly limited to destructive top-down processes such as heating, ion bombardments, and laser postprocessing. Here, we introduce a single-step bottom-up synthesis approach for the growth of monolayer MoSe 2 crystals with tunable vacancy concentrations. This method utilizes the spatiotemporal properties and adjustable power densities of the lasers to control the vaporization dynamics of the stoichiometric MoSe 2 powders. Such a mechanism in the vaporization allows us to grow tunable stoichiometry monolayer MoSe 2–x crystals on the substrates. The localized and time-controlled (250 ms to 2 s) vaporization of the MoSe 2 powder by a CO 2 laser enables the formation of monolayer crystals with controlled vacancy concentrations ranging from ~1 to 20%. The effects of laser power, laser irradiation time, and background pressure on the tuning range and subsequent properties of the crystals are investigated and quantified using Raman and photoluminescence spectroscopy, scanning transmission electron microscopy (STEM), and time-correlated single-photon counting (TCSPC). This bottom-up synthesis is a promising approach that allows the deterministic vacancy tuning for future electronics and, in particular, gas and biosensing applications without the need for further postprocessing and potential structural disruption of the crystals.

2D materials↗

A single-photon lidar observes atmospheric clouds at decimeter scales: resolving droplet activation within cloud base

Abstract Clouds, crucial for understanding climate, begin with droplet formation from aerosols, but observations of this fleeting activation step are lacking in the atmosphere. Here we use a time-gated time-correlated single-photon counting lidar to observe cloud base structures at decimeter scales. Results show that the air–cloud interface is not a perfect boundary but rather a transition zone where the transformation of aerosol particles into cloud droplets occurs. The observed distributions of first-arriving photons within the transition zone reflect vertical development of a cloud, including droplet activation and condensational growth. Further, the highly resolved vertical profile of backscattered photons above the cloud base enables remote estimation of droplet concentration, an elusive but critical property to understanding aerosol–cloud interactions. Our results show the feasibility of remotely monitoring cloud properties at submeter scales, thus providing much-needed insights into the impacts of atmospheric pollution on clouds and aerosol-cloud interactions that influence climate.

54 ENVIRONMENTAL SCIENCES↗

Spectral characterization of an SPDC source with a fast broadband spectrometer

Knowing the properties of single photons produced in a Spontaneous Parametric Down-Conversion (SPDC) source can be crucial for specific applications and uses. In particular, the spectral properties are of key relevance. Here, we investigate a commercial SPDC source using our fast broadband spectrometer. Our analysis is a valid method for other SPDC sources, as well as other single-photon generation techniques, thus providing a good example of how to use this spectrometer design. We calibrate the spectrometer using known lines of the argon emission spectrum. We show that the two down-converted photons from the SPDC source have different spectral properties depending on the pump power, and under which condition we measured spectrally similar down-converted photons. Finally, we were able to reconstruct and investigate the spectral information for the pump photon.

79 ASTRONOMY AND ASTROPHYSICS↗

High-resolution lidar observations of sedimentation-induced size sorting of droplets near a laboratory cloud top

Cloud optical properties and precipitation, which are crucial to weather and climate, are strongly influenced by cloud microphysical properties that are still poorly understood. Here, we develop a high-resolution time-correlated single-photon-counting lidar and apply it to observe cloud microphysical properties at one-centimeter range resolution in a convection chamber under well-controlled conditions. Together with concurrent in-situ measurements and theoretical analysis, our lidar observations indicate that although turbulent mixing tends to homogenize the cloud in the bulk region, entrainment and sedimentation cause inhomogeneities in droplet concentrations near the cloud top. Specifically, the topmost region is directly affected by entrainment, and lidar profiles show clear evidence of entrained air and detrained cloud filament. The transition region below exhibits vertical size sorting of cloud droplets caused by sedimentation. Our results suggest that using a single sedimentation velocity for all cloud droplets, as is done in many atmospheric models, overlooks key physics relevant to the microphysical structure near the cloud top. In conclusion, our conceptual model used to describe these measurements can serve as a step toward improving the current modeling of processes in the cloud top region.

54 ENVIRONMENTAL SCIENCES↗