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At least 811 records · Page 45

Extracting the electronic structure of light elements in bulk materials through a Compton scattering method in the readily accessible hard x-ray regime

Here, our Compton profile measurements of Ti and TiH 2 using readily available hard X-ray radiation at 27.5 keV, detected by both a Hitachi Vortex silicon-drift detector and a high-resolution superconducting transition-edge sensor array, are found to be in excellent accord with state-of-the-art density functional theory based calculations. The spherically averaged difference between the Compton profiles of TiH 2 and Ti is well described by an inverted parabola, supporting an itinerant behavior of the electron gas screening the protons in the Ti matrix. Our experimental approach, validated by two different detectors, extends the applicability of Compton scattering technique to the readily accessible hard x-ray regime (below 30 keV). Our study suggests possibilities for experiments at low-flux bending magnet synchrotron beamlines and paves the way for the development of tabletop Compton experiments with x-ray tubes.

36 MATERIALS SCIENCE↗

Anti-polyelectrolyte and polyelectrolyte effects on conformations of polyzwitterionic chains in dilute aqueous solutions

Abstract Polyzwitterions (PZs) are considered as model synthetic analogs of intrinsically disordered proteins. Based on this analogy, PZs in dilute aqueous solutions are expected to attain either globular (i.e. molten, compact) or random coil conformations. Addition of salt is expected to open these conformations. To the best of our knowledge, these hypotheses about conformations of PZs have never been verified. In this study, we test these hypotheses by studying effects of added salt [potassium bromide (KBr)] on gyration and hydrodynamic radii of poly(sulfobetaine methacrylate) in dilute aqueous solutions using dynamic light scattering and small-angle X-ray scattering, respectively. Effects of zwitteration are revealed by direct comparisons of the PZs with the polymers of the same backbone but containing (1) no explicit charges on side groups such as poly(2-dimethylaminoethyl methacrylate)s and (2) explicit cationic side groups with tertiary amino bromide pendants. Zeta-potential measurements, transmission electron microscopy, and ab initio molecular dynamics simulations reveal that the PZs acquire net positive charge in near salt-free conditions due to protonation but retain coiled conformations. Added KBr leads to nonmonotonic changes exhibiting an increase followed by a decrease in radius of gyration (and hydrodynamic radius), which are called antipolyelectrolyte and polyelectrolyte effects, respectively. Charge regulation and screening of charge–charge interactions are discussed in relation to the antipolyelectrolyte and polyelectrolyte effects, respectively, which highlight the importance of salt in affecting net charge and conformations of PZs.

36 MATERIALS SCIENCE↗

Giant isotope effect on phonon dispersion and thermal conductivity in methylammonium lead iodide

Lead halide perovskites are strong candidates for high-performance low-cost photovoltaics, light emission, and detection applications. A hot-phonon bottleneck effect significantly extends the cooling time of hot charge carriers, which thermalize through carrier–optic phonon scattering, followed by optic phonon decay to acoustic phonons and finally thermal conduction. To understand these processes, we adjust the lattice dynamics independently of electronics by changing isotopes. We show that doubling the mass of hydrogen in methylammonium lead iodide by replacing protons with deuterons causes a large 20 to 50% softening of the longitudinal acoustic phonons near zone boundaries, reduces thermal conductivity by ~50%, and slows carrier relaxation kinetics. Phonon softening is attributed to anticrossing with the slowed libration modes of the deuterated molecules and the reduced thermal conductivity to lowered phonon velocities. Our results reveal how tuning the organic molecule dynamics enables control of phonons important to thermal conductivity and the hot-phonon bottleneck.

36 MATERIALS SCIENCE↗

NASAs Evolvable Mars Campaign: Mars Moons Robotic Precursor

Human exploration missions to the moons of Mars are being considered within NASA's Evolvable Mars Campaign (EMC) as an intermediate step for eventual human exploration and pioneering of the surface of Mars. A range of mission architectures is being evaluated in which human crews would explore one or both moons for as little as 14 days or for as long as 500 days with a variety of orbital and surface habitation and mobility options being considered. Relatively little is known about the orbital, surface, or subsurface characteristics of either moon. This makes them interesting but challenging destinations for human exploration missions during which crewmembers must be able to effectively conduct scientific exploration without being exposed to undue risks due to radiation, dust, micrometeoroids, or other hazards. A robotic precursor mission to one or both moons will be required to provide data necessary for the design and operation of subsequent human systems and for the identification and prioritization of scientific exploration objectives. This paper identifies and discusses considerations for the design of such a precursor mission based on current human mission architectures. Objectives of a Mars' moon precursor in support of human missions are expected to include: 1) identifying hazards on the surface and the orbital environment at up to 50-km distant retrograde orbits; 2) collecting data on physical characteristics for planning of detailed human proximity and surface operations; 3) performing remote sensing and in situ science investigations to refine and focus future human scientific activities; and 4) prospecting for in situ resource utilization. These precursor objectives can be met through a combination or remote sensing (orbital) and in-situ (surface) measurements. Analysis of spacecraft downlink signals using radio science techniques would measure the moon's mass, mass distribution, and gravity field, which will be necessary to enable trajectory planning. Laser altimetry would precisely measure the moon's shape and improve the accuracy of radio science measurements. A telescopic imaging camera would map the moon at submeter resolution and photograph selected areas of interest at subcentimeter resolution and a visible and near-infrared (0.4-3.0 mm) imaging spectrograph would produce a global map of mineral composition variations at a resolution of tens of meters and maps of selected areas of interest at meter resolution. Additional remote sensing capabilities could include a thermal infrared imager (heat flow, thermal inertia, and grain size distributions), a gamma-ray and neutron detector (atomic composition), a ground-penetrating radar (internal structure), and a magnetometer and Langmuir probe (magnetic properties and plasma field). Once on the surface of Phobos or Deimos, necessary instrumentation would include a penetrometer (regolith compressive strength), a motion-imagery camera (to observe the penetrometer tests before, during, and after contact), a dust-adhesion witness plate and camera (dust levitation), a microimager (dust particle sizes and shapes), and an alpha-proton-X-ray, X-ray fluorescence, Mossbauer, or Raman spectrometer (atomic and mineral composition of surface materials) and an optional temperature probe (regolith thermal properties). A variety of robotic mission design options to enable both orbital and surface measurements are being considered that include fully integrated and modular approaches. In-situ measurements from at least one surface location would be required, with additional measurement locations possible through use of multiple landers, through propulsive relocation of a single lander, or through electromechanical surface translation by a walking or hopping lander vehicle, which could also serve to evaluate such mobility capabilities for subsequent human missions. Preliminary orbital analysis suggests that remote sensing would likely be performed while in a distant retrograde orbit around the target moon. Mission design options to enable characterization of both Mars’ moons in a single mission are also being studied.

Gernhardt, Michael L.↗

Science Prospects from the STEREO Mission

The solar magnetic field is constantly generated beneath the surface of the Sun by the solar dynamo. To balance this flux generation, there is constant dissipation of magnetic flux at and above the solar surface. The largest phenomenon associated with this dissipation is the Coronal Mass Ejection (CME). The Solar and Heliospheric Observatory (SOHO) has provided remarkable views of the corona and CMEs, and served to highlight how these large interplanetary disturbances can have terrestrial consequences. STEREO is the next logical step to study the physics of CME origin, propagation, and terrestrial effects. Two spacecraft with identical instrument complements will be launched on a single launch vehicle in November 2007. One spacecraft will drift ahead and the second behind the Earth at a separation rate of 22 degrees per year. Observation from these two vantage points will for the first time allow the observation of the three-dimensional structure of CMEs and the coronal structures where they originate. Each STEREO spacecraft carries a complement of 10 instruments, which include (for the first time) an extensive set of BOTH remote sensing and in-situ instruments. The remote sensing suite is capable of imaging CMEs from the solar surface out to beyond Earth's orbit (1 AU), and in-situ instruments are able to measure distribution functions for electrons, protons, and ions over a broad energy range, from the normal thermal solar in wind plasma to the most energetic solar particles. It is anticipated that these studies will ultimately lead to an increased understanding, of the CME process and eventually to the ability to predict CME occurrence and thereby 'forecast' the condition of the near-Earth environment.

Davila, Joseph M.↗

Novel Hydrogen Clathrate Hydrate

We report a new hydrogen clathrate hydrate synthesized at 1.2 GPa and 298 K documented by single-crystal x-ray diffraction, Raman spectroscopy, and first-principles calculations. The oxygen sublattice of the new clathrate hydrate matches that of ice II, while hydrogen molecules are in the ring cavities, which results in the trigonal R3c or R¯3c space group (proton ordered or disordered, respectively) and the composition of ( H 2 O) 6 H 2 . Raman spectroscopy and theoretical calculations reveal a hydrogen disordered nature of the new phase $C$$^{'}_{1}$, distinct from the well-known ordered C 1 clathrate, to which this new structure transforms upon compression and/or cooling. Furthermore, this new clathrate phase can be viewed as a realization of a disordered ice II, unobserved before, in contrast to all other ordered ice structures.

36 MATERIALS SCIENCE↗

A data-driven method to estimate contamination from light ion beam transmutation at colliders

Collisions of relativistic light ions such as oxygen, neon, and magnesium, have been proposed as a way to examine the system-size dependence of dynamics typically associated with the quark-gluon plasma produced in collisions of heavier ions such as xenon, gold, or lead. Recent efforts at both the Relativistic Heavy Ion Collider (RHIC) and Large Hadron Collider (LHC) have produced large datasets of proton-oxygen, oxygen-oxygen, and neon-neon collisions, catalyzing intense interest in experimental backgrounds associated with light ion collisions. In particular, electromagnetic dissociation of light ions while they are circulating in a collider can result in beam contamination that is difficult to simulate precisely. Here we propose a data-driven method for evaluating the potential impact of beam contaminants on physics analyses. The method exploits the time-dependence and smaller size of contaminant ion species to define control regions that can be used to quantify potential contamination effects. A simple mode

Accelerator Physics (physics.acc-ph)↗

Atom Probe Tomography for understanding microstructural and chemical changes in nuclear materials

Atom Probe Tomography (APT) is routinely employed to determine 3D microstructure and chemistry changes in structural materials used in reactor to understand irradiation effect. These findings help to correlate changes to mechanical and physical properties of nuclear materials which are subjected to extreme reactor conditions. With safety and economics of a reactor in mind, it is essential to be able to predict the changes in the fuel composition and microstructure as a function of burnup. Also, there is current need to develop advanced fuels with improved properties and performance which requires the experimental data on changes in microstructure, physical and chemical properties after irradiation for feedback process. A novel approach is presented to determine the local burnup in irradiated fuels using isotopic quantification obtained by Atom Probe Tomography (APT). Considering the volume of sample used (<100?µm3) for APT experiments using the lift-out process in a scanning electron microscope equipped with a Focused Ion Beam (FIB), the presented method determines the local burnup from a nuclear fuel, where a minimal amount of waste is produced. In this work, three samples were analyzed with different burnup conditions to quantify the isotopes of 235U, 236U, and 238U for burnup calculation in the irradiated metallic U–7Mo dispersion fuel. The calculated values were found in excellent agreement with MCNP calculations. With regard to structural materials, one of the primary factors limiting the utilization of fuel rods of Zr alloys is hydrogen pick up during oxidation. Past experimental studies have shown that the hydrogen pickup in Zirconium alloys is influenced by the alloy composition as well by irradiation temperature and neutron dose. Oftentimes, it is not feasible to carry out comprehensive studies on understanding the microstructural evolution in neutron irradiated materials since in reactor irradiation programs are extremely costly, lengthy and logistically complicated. The use of ion irradiation as a substitute has grown in recent years for several reasons including less radioactivity, faster irradiations and lower costs. In the framework of the MUZIC 3 project, samples of Zircaloy-4 have been proton and Zr2+ irradiated at the Michigan Ion Beam Lab (MIBL) facility with aim to create a microstructure that is similar to that observed after in-reactor service. The temperature of the environment is adjusted to compensate for the higher dose rate, as has been done previously. As a first step in this project the irradiated microstructures have been characterized using Transmission Electron Microscopy and Atom Probe Tomography to elucidate the microstructural changes, including precipitate amorphization and dissolution and the formation of dislocation loops. This presentation plans to highlight initial finding of this project.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Cell-Free Systems Biology: Characterizing Central Metabolism of Clostridium thermocellum with a Three-Enzyme Cascade Reaction

Genetic approaches have been traditionally used to understand microbial metabolism, but this process can be slow in nonmodel organisms due to limited genetic tools. An alternative approach is to study metabolism directly in the cell lysate. This avoids the need for genetic tools and is routinely used to study individual enzymatic reactions but is not generally used to study systems-level properties of metabolism. Here we demonstrate a new approach that we call “cell-free systems biology”, where we use well-characterized enzymes and multienzyme cascades to serve as sources or sinks of intermediate metabolites. This allows us to isolate subnetworks within metabolism and study their systems-level properties. To demonstrate this, we worked with a threeenzyme cascade reaction that converts pyruvate to 2,3-butanediol. Although it has been previously used in cell-free systems, its pH dependence was not well characterized, limiting its utility as a sink for pyruvate. We showed that improved proton accounting allowed better prediction of pH changes and that active pH control allowed 2,3-butanediol titers of up to 2.1 M (189 g/L) from acetoin and 1.6 M (144 g/L) from pyruvate. The improved proton accounting provided a crucial insight that preventing the escape of CO 2 from the system largely eliminated the need for active pH control, dramatically simplifying our experimental setup. We then used this cascade reaction to understand limits to product formation in Clostridium thermocellum, an organism with potential applications for cellulosic biofuel production. We showed that the fate of pyruvate is largely controlled by electron availability and that reactions upstream of pyruvate limit overall product formation.

09 BIOMASS FUELS↗

Understanding Proton Movement in [Fe-Fe] Hydrogenases

Nature uses specialized metalloenzymes to carry out small molecule activation reactions, including CO 2 fixation, O 2 activation, and proton reduction, with unparalleled efficiency, rates, and selectivity. The latter reactions are performed by hydrogenases, protein metallo-complexes that interconverts H 2 to protons and electrons (H 2 oxidation) and the reverse reaction (H 2 production) with incredibly low energy input and amazingly fast kinetics. Reproducing both the activity and efficiency of metalloenzymes in sustainable anthropogenic systems remains one of the “holy grails” of inorganic chemistry. However, identifying the precise molecular components responsible for these desirable properties has been challenging in the natural metalloenzymes, hindering efforts to develop analogous processes in synthetic compounds. Considering the inherent complexity of a metalloenzyme and the many interactions, both strong and weak, that contribute to the function of an enzyme, we have elected to model natural metalloenzymes on a biochemical platform. Towards this end, we have a developed structural, functional, and mechanistic mimic of the [Ni-Fe] hydrogenases within a robust protein scaffold, rubredoxin, to understand the influence of the secondary coordination environment on the metal center. This involved preparing a series of three rubredoxin constructs containing a single point mutation at Val positions and making the NMR chemical shift assignments for the paramagnetic (nickel-substituted) and non-paramagnetic (zinc-substituted) form. These physical studies were complemented with in silico molecular dynamic studies on proteins with [Fe-S] clusters to engineer new proton channels to test in vitro . To assist our search for new natural metalloprotein scaffolds within the vast number of sequenced genomes, we created a neural network-based program to identify proteins with specific metal-binding sites. These computational and physical studies with metalloenzymes provide direct insight into the fundamental chemical principles driving the natural systems and offer design principles for developing catalysts that utilize analogous principles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Mu2e crystal calorimeter

The Mu2e experiment at Fermilab will search for the charged-lepton flavour violating conversion of negative muons into electrons in the coulomb field of an Al nucleus, planning to reach a single event sensitivity of about $3\cdot10^{−17}$, four orders of magnitude beyond the current best limit.The conversion electron has a clear monoenergetic signature at 104.967 MeV, slightly below the muon rest mass, and will be identified by a complementary measurement carried out by a high-resolution tracker and an electromagnetic calorimeter (EMC). The calorimeter is composed of 1348 pure CsI crystals, each read by two custom UV-extended SiPMs, that are arranged in two annular disks. The EMC should achieve better than 10% energy resolution and 500 ps timing resolution for 100 MeV electrons and maintain extremely high levels of reliability and stability and in a harsh operating environment with high vacuum, 1 T B-field and radiation exposures up to 100 krad and $10^{12} \rm{n}_\rm{1MeVeq}/\rm{cm}^{2}$.The calorimeter technological choice, along with the design of the custom front-end electronics, cooling and mechanical systems were validated through an electron beam test on a large-scale 51-crystals prototype (Module-0) and extensive test campaigns that characterised and verified the performance of crystals, photodetectors, analogue and digital electronics. This included hardware stress tests and irradiation campaigns with neutrons, protons, and photons.The production and QC phases of all calorimeter components is completed apart for the digital electronics that has been revised for improving its resilience to SEU and SEL. A series of vertical slice tests with the final electronics is being carried out on the Module-0 at LNF along with the implementation and validation of the calibration procedures. The first disk has been assembled in 2022 while the second disk is under assembly at the moment of writing. Status of construction will be summarised, along with plans for commissioning and first calibration of the fully assembled disks.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Proton-rich Production of Lanthanides: The vi Process

The astrophysical origin of the lanthanides is an open question in nuclear astrophysics. Besides the widely studied s, i, and r processes in moderately to strongly neutron-rich environments, an intriguing alternative site for lanthanide production could in fact be robustly proton-rich matter outflows from core-collapse supernovae under specific conditions—in particular, high-entropy winds with enhanced neutrino luminosity and fast dynamical timescales. In this environment, excess protons present after charged-particle reactions have ceased can continue to be converted to neutrons by (anti)neutrino interactions, producing a neutron-capture reaction flow up to A ∼ 200. This scenario, christened the νi process in a recent paper, has previously been discussed as a possibility. Here, we examine the prospects for the νi process through the lenses of stellar abundance patterns, bolometric light curves, and galactic chemical evolution models, with a particular focus on hypernovae as candidate sites. We identify specific lanthanide signatures for which the νi process can provide a credible supplement to the r/i processes.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Initial-site characterization of hydrogen migration following strong-field double-ionization of ethanol

Abstract An essential problem in photochemistry is understanding the coupling of electronic and nuclear dynamics in molecules, which manifests in processes such as hydrogen migration. Measurements of hydrogen migration in molecules that have more than two equivalent hydrogen sites, however, produce data that is difficult to compare with calculations because the initial hydrogen site is unknown. We demonstrate that coincidence ion-imaging measurements of a few deuterium-tagged isotopologues of ethanol can determine the contribution of each initial-site composition to hydrogen-rich fragments following strong-field double ionization. These site-specific probabilities produce benchmarks for calculations and answer outstanding questions about photofragmentation of ethanol dications; e.g., establishing that the central two hydrogen atoms are 15 times more likely to abstract the hydroxyl proton than a methyl-group proton to form H $${}_{3}^{+}$$ 3 + and that hydrogen scrambling, involving the exchange of hydrogen between different sites, is important in H 2 O + formation. The technique extends to dynamic variables and could, in principle, be applied to larger non-cyclic hydrocarbons.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Correlation between backbone and pyridine dynamics in poly(2-vinyl pyridine)/silica polymer nanocomposites

Polymer segmental dynamics in polymer nanocomposites (PNCs) can be significantly perturbed from bulk and underly macroscopic material properties such as mechanical enhancements and improved small molecule transport, but fundamental studies are necessary to further understand this concept. To elucidate a mechanistic description of this perturbation and isolate different molecular motions, we present quasi-elastic neutron scattering (QENS) measurements on PNCs with attractive interactions comprised of colloidal silica nanoparticles (NPs) uniformly dispersed in poly(2-vinyl pyridine) (P2VP) with and without backbone deuteration. Measurements of fully-protonated P2VP probe the dynamics of both the polymer backbone and pyridine pendant group, whereas measurements of backbone deuterated P2VP isolate the dynamics of only the pyridine ring. On the small length scales (~1 nm) and fast time scales (~1 ns) captured by QENS, we show that the backbone and pyridine ring dynamics are highly coupled at high temperature and both are slowed by about 35% relative to neat polymer in 25 vol% PNCs. This observation implies that the backbone and pendant interfacial dynamics are perturbed similarly in PNCs, which further develops our fundamental understanding of microscopic properties in PNCs.

36 MATERIALS SCIENCE↗

Studying the Role of a Single Mutation of a Family 11 Glycoside Hydrolase Using High-Resolution X-ray Crystallography

XynII is a family 11 glycoside hydrolase that uses the retaining mechanism for catalysis. In the active site, E177 works as the acid/base and E86 works as the nucleophile. Mutating an uncharged residue (N44) to an acidic residue (D) near E177 decreases the enzyme’s optimal pH by ~ 1.0 unit. D44 was previously suggested to be a second proton carrier for catalysis. To test this hypothesis, we abolished the activity of E177 by mutating it to be Q, and mutated N44 to be D or E. These double mutants have dramatically decreased activities. Our high-resolution crystallographic structures and the microscopic pK a calculations show that D44 has similar position and pK a value during catalysis, indicating that D44 changes electrostatics around E177, which makes it prone to rotate as the acid/base in acidic conditions, thus decreases the pH optimum. Our results could be helpful to design enzymes with different pH optimum.

59 BASIC BIOLOGICAL SCIENCES↗

Isotope-dependent Tafel analysis probes proton transfer kinetics during electrocatalytic water splitting

Proton transfer plays an important role in both hydrogen and oxygen evolution reactions during electrocatalytic water splitting to produce green hydrogen. However, directly adapting the conventional proton/deuterium kinetic isotope effect to study proton transfer in heterogeneous electrocatalytic processes is challenging. Here we propose using the shift in the Tafel slope between protic and deuteric electrolytes, or the Tafel slope isotope effect, as an effective probe of proton transfer characteristics. Comparison of the Tafel slope isotope effect for diverse hydrogen and oxygen evolution reaction electrocatalysts in different pH environments reveals that proton transfer is both pH and structure dependent. Using ruthenium oxide as an example, we show that local structure modification can change the rate-determining step from an electrochemical, concerted proton–electron transfer step to a chemical step and improve the oxygen evolution activity in acid. The isotope-dependent Tafel analysis will facilitate a better understanding of the proton transfer behaviours during electrocatalytic processes and provide guidance for designing efficient electrocatalysts.

Chemistry↗

Impact of modifier-rich coatings on the ionic transport of glasses [Poster]

Ionic conduction in silicate glasses is mainly influenced by the nature, concentration, and mobility of the network-modifying (NWM) cations. The electrical conduction in SLS is dominated by the ionic migration of sodium moving from the anode to the cathode. An activation energy for this conduction process was calculated to be 0.82eV and in good agreement with values previously reported. The conduction process associated to the leakage current and relaxation peak in TSDC for HPFS is attributed to conduction between nonbridging oxygen hole centers (NBOHC). It is suggested that ≡Si-OH = ≡Si-O - + H 0 under thermo-electric poling, promoting hole or proton injection from the anode and responsible for the 1.5eV relaxation peak. No previous TSDC data have been found to corroborate this mechanism. The higher activation energy and lower current intensity for the coated HPFS might be attributed to a lower concentration of NBOHC after heat treatment (Si-OH + OH-Si = SiO-Si + H 2 O). This could explain the TSDC signal around room temperature for the coated HPFS. Another possible explanation could be a redox reaction at the anode region dominating the current response.

36 MATERIALS SCIENCE↗

EPCAPE – Proton Transfer Reaction Mass Spectrometer Field Campaign Report

The Eastern Pacific Cloud Aerosol Precipitation Experiment – Proton Transfer Reaction Mass Spectrometer (EPCAPE-PTRMS) campaign was created in response to the urgent need expressed by EPCAPE co-investigators for measurements of volatile organic compounds (VOCs) during the EPCAPE intensive operational period. A proton transfer reaction time-of-flight mass spectrometer (PTR-ToF-MS, model 8000, Ionicon Analytik) was deployed to Mt. Soledad, San Diego, California, on 15 May 2023 for the measurement of VOCs. The instrument was installed in the same Atmospheric Radiation Measurement (ARM) user facility guest container that the Smith group used for the EPCAPE – Ultrafine Particle Properties (EPCAPE-UPP) campaign. The Smith group provided the sample inlet and operated and maintained the instrument. A complete VOC mass spectrum was recorded every 10 sec, continuously. Calibrations using a traceable VOC mixture were performed onsite at the end of the campaign.

54 ENVIRONMENTAL SCIENCES↗