222 nm Far-UVC from filtered Krypton-Chloride excimer lamps does not cause eye irritation when deployed in a simulated office environment.

Far-UVC, from filtered Krypton-Chloride lamps, is promising for reducing airborne transmission of disease. While significant research has been undertaken to investigate skin safety of these lamps, less work has been undertaken on eye safety. There is limited data on human eye safety or discomfort from the deployment of this germicidal technology. In this pilot study, immediate and delayed eye discomfort were assessed in a simulated office environment with deployment of Krypton-Chloride lamps, located on the ceiling and directed downwards into the occupied room. Discomfort was assessed immediately postexposure and several days after exposure using validated, Standard Patient Evaluation Eye Dryness (SPEED) and Ocular Surface Disease Index (OSDI) questionnaires. Our results show no significant eye discomfort or adverse effects from the deployment of Far-UVC in this simulated office environment, even when lamps were operated continuously with participants receiving head exposures of up to 50 mJ cm-2 . In addition, a statistically significant reduction in bacteria and fungi of 52% was observed. Far-UVC in this simulated office environment did not cause any clinically significant eye discomfort and was effective at reducing pathogens in the room. These results contribute an important step to further investigation of the interaction of Far-UVC with the human eye.

Validation of krypton as a new tracer gas for the standardization tests of collective and individual protection systems.

Sulfur hexafluoride (SF6) is the reference tracer gas in many international standards for characterizing respiratory protective devices (RPD), fume cupboards, building ventilations, and other installations. However, due to its significant impact on global warming, its use is becoming increasingly restrictive. Krypton 84 (Kr) was chosen to be a possible replacement based on theoretical and practical criteria for the properties that a substitute gas should possess. While compliance with these criteria is generally sufficient to guarantee the reliability of the choice, it is essential in the case of widespread use such as a standard to validate experimentally that this tracer has the same behavior as SF6. In this regard, numerous tests have been carried out to characterize the face leakage of RPD and the rupture of containment of fume cupboards performance tests under different operating conditions. The results obtained are identical with both tracers and lead us to propose the use of Kr as a new reference gas in standards for which SF6 was used.

Structure, energetics, and spectroscopy of the K2+(X2Σ+g) interacting with the noble gas atoms Ar, Kr and Xe.

The structure, energetic, and spectroscopy properties of the ionic system K2+(X2Σ+g) interacting with the noble gas atoms Argon, Krypton and Xenon are studied. The computations are done by an accurate ab initio approach based on the pseudo-potential technique, Gaussian basis sets, parameterized l-dependent polarization potentials and an analytic potential form for the K+Ar, K+Kr and K+Xe interactions. These interactions are added via the CCSD(T) potential taken from literature and fitted applying the analytical expression of Tang and Toennies. The application of the pseudo-potential approach reduces the number of active electrons of each complex to only one electron. The potential energy surfaces are analyzed on a large range of the Jacobi coordinates, R and θ. By the general interpolation outline based on the RKHS (Reproducing Kernel Hilbert Space) procedure, we have reproduced for each complex from our ab initio results the two-dimensional contour plots of an analytical potential. To evaluate the stability of each complex, we have determined from the potential energy surfaces the equilibrium distance (Re), the well depth (De), the quantum energy (D0), the zero-point-energy (ZPE) and the ZPE%. The results showed that the linear configurations, where the noble gas atom connected to the K2+(X2Σ+g) system, are the more stable.

Identifying medically relevant xenon protein targets by in silico screening of the structural proteome.

In a previous study, in silico screening of the binding of almost all proteins in the Protein Data Bank to each of the five noble gases xenon, krypton, argon, neon, and helium was reported. This massive and rich data set requires analysis to identify the gas-protein interactions that have the best binding strengths, those where the binding of the noble gas occurs at a site that can modulate the function of the protein, and where this modulation might generate clinically relevant effects. Here, we report a preliminary analysis of this data set using a rational, heuristic score based on binding strength and location. We report a partial prioritized list of xenon protein targets and describe how these data can be analyzed, using arginase and carbonic anhydrase as examples. Our aim is to make the scientific community aware of this massive, rich data set and how it can be analyzed to accelerate future discoveries of xenon-induced biological activity and, ultimately, the development of new "atomic" drugs.

UV Inactivation of Common Pathogens and Surrogates Under 222 nm Irradiation from KrCl* Excimer Lamps.

Germicidal ultraviolet (UV) devices have been widely used for pathogen disinfection in water, air, and on food and surfaces. Emerging UV technologies, like the krypton chloride (KrCl*) excimer emitting at 222 nm, are rapidly gaining popularity due to their minimal adverse effects on skin and eyes compared with conventional UV lamps emitting at 254 nm, opening opportunities for UV disinfection in occupied public spaces. In this study, inactivation of seven bacteria and five viruses, including waterborne, foodborne and respiratory pathogens, was determined in a thin-film aqueous solution using a filtered KrCl* excimer emitting primarily at 222 nm. Our results show that the KrCl* excimer can effectively inactivate all tested bacteria and viruses, with most microorganisms achieving more than 4-log (99.99%) reduction with a UV dose of 10 mJ cm-2 . Compared with conventional UV lamps, the KrCl* excimer lamp exhibited better disinfection performance for viruses but was slightly less effective for bacteria. The relationships between UV sensitivities at 222 and 254 nm for bacteria and viruses were evaluated using regression analysis, resulting in factors that could be used to estimate the KrCl* excimer disinfection performance from well-documented UV kinetics using conventional 254 nm UV lamps. This study provides fundamental information for pathogen disinfection when employing KrCl* excimers.

Synergistic disinfection of aerosolized bacteria and bacteriophage by far-UVC (222-nm) and negative air ions.

Air ionizers and 222-nm krypton-chlorine (KrCl) excilamp have proven to be effective disinfection apparatus for bacteria and viruses with limited health risks. We determined inactivation efficiencies by operating them individually and in combined modules. Gram-positive and gram-negative bacteria, non-enveloped dsDNA virus, and enveloped dsRNA virus were examined in a designed air disinfection system. Our results showed that the bioaerosols were inactivated efficiently by negative ionizers and far-UVC (222-nm), either used individually or in combination. Among which the combined modules of negative ionizers and KrCl excilamp had the best disinfection performance for the bacteria. The aerosolized virus P22 and Phi 6 were more susceptible to 222-nm emitted by KrCl excilamp than negative air ions. Significant greater inactivation of bacterial bioaerosols were identified after treated by combined treatment of negative air ion and far-UVC for 2 minutes (Escherichia coli, 6.25 natural log (ln) reduction; Staphylococcus epidermidis, 3.66 ln reduction), as compared to the mean sum value of inactivation results by respective individual treatment of negative ionizers and KrCl excilamp (Escherichia coli, 4.34 ln; Staphylococcus epidermidis, 1.75 ln), indicating a synergistic inactivation effect. The findings provide important baseline data to support the design and development of safe and high-efficient disinfection systems.

Potential harm to the skin from unfiltered krypton chloride 'far-ultraviolet-C' lamps, even below an occupational exposure limit.

Ultraviolet-C (UVC) radiation can effectively inactivate pathogens on surfaces and in the air. Due to the potential for harm to skin and eyes, human exposure to UVC should be limited within the guideline exposure limits produced by the International Commission on Non-Ionising Radiation Protection (ICNIRP) or the American Conference of Governmental Industrial Hygienists (ACGIHs). Both organisations state an effective spectrally weighted limit of 3 mJ cm-2, although the spectral weighting factors of the two organisations diverged following a revision of the ACGIH guidelines in 2022. Using existing published human exposure data, the effective spectrally weighted radiant exposure was calculated for both unfiltered and filtered (to reduce UV emissions above 230 nm) krypton chloride (KrCl*) excimer lamps. The effective radiant exposure of the filtered KrCl* lamp was greater than 3 mJ cm-2when applying ICNIRP or either of the revised ACGIH spectral weightings. This indicates that both guidelines are appropriately conservative for this specific lamp. However, the effective radiant exposure of the unfiltered KrCl* lamp was as low as 1 mJ cm-2with the revised ACGIH weighting function that can be applied to the skin if the eyes are protected. Erythema has therefore been directly observed in a clinical study at an exposure within the revised ACGIH guideline limits. Extrapolating this information means that a mild sunburn could be induced in Fitzpatrick skin types I and II if that particular ACGIH weighting function were applied and an individual received an effective exposure of 3 mJ cm-2. Whilst it is improbable that such an effect would be seen in current deployment of KrCl* lamp technology, it does highlight the need for further research into skin sensitivity and irradiance-time reciprocity for UVC wavelengths.

Developments of a field gas extraction device and krypton purification system for groundwater radio-krypton dating at the IAEA.

The long-lived radio-krypton isotope 81Kr (t1/2 = 2.29 × 105 yr) is an ideal tracer for old groundwater age dating in the range of 105-106 years which goes beyond the reach of radio-carbon (14C) age dating. Analytical breakthrough made over the last two decades in Atom Trap Trace Analysis (ATTA) has enabled the use of this isotope with extremely low abundance (81Kr/Kr = 6 × 10-13) to be used as a practical dating tool for very old groundwater. The International Atomic Energy Agency aims to provide this new isotope tool for better groundwater resource management of Member States and developed a field sampling device to collect dissolved gas samples from groundwater and a system to separate and purify trace amounts of krypton from the gas samples for the ATTA analysis. The design, setup and performances of our sampling and purification systems are described here. Our system can produce a high purity aliquot of about 5 µL of krypton from 5 L of air sample (recovery yield of >90%). The samples made by our system were confirmed to be acceptable for the ATTA analysis.

Monitoring Noble Gases (Xe and Kr) and Aerosols (Cs and Rb) in a Molten Salt Reactor Surrogate Off-Gas Stream Using Laser-Induced Breakdown Spectroscopy (LIBS).

This study with surrogate materials shows that laser-induced breakdown spectroscopy (LIBS) is a robust tool with promising capability toward monitoring gaseous (Xe and Kr) and aerosol (Cs and Rb) species in an off-gas stream from a molten salt reactor (MSR). MSRs will continually evolve fission products into the cover gas flowing across the reactor headspace. The cover gas entrains Xe and Kr gases, along with aerosol particles, before passing into an off-gas treatment system. Univariate models of Xe and Kr peaks showed a strong correlation to concentration indicated by their coefficients of determination of 0.983 and 0.997, respectively. Multivariate models were built for all four analytes using partial least squares regression coupled with preprocessing steps including normalization, trimming, and/or genetic algorithm derived filters. The models were evaluated by predicting the concentrations of the analytes in four validation samples, in which all calibration models were successfully validated at a confidence interval of 99.9%. Lastly, pressure controllers were used to regulate the mass flow rate of Kr flowing into the measurement cell in sinusoidal and stepwise waveforms to test the real-time monitoring capabilities of the regression models. Both univariate and partial least squares Kr models were able to successfully quantify the gas concentration in the real-time evaluation. The root mean squared error of prediction (RMSEP) values for these real-time tests were calculated to be 0.051, 0.060, and 0.121 mol% demonstrating the measurement systems' capability to perform online monitoring with acceptable accuracy.

Effect of ultraviolet C emitted from KrCl excimer lamp with or without bandpass filter to mouse epidermis.

It has been reported that 222-nm ultraviolet C (UVC) exerts a germicidal effect on bacteria and viruses as well as UV radiation emitted from a conventional germicidal lamp but is less toxic to the mammalian cells than that from a germicidal lamp. An excimer lamp filled with krypton chloride (KrCl) gas principally emits 222-nm UVC. However, the lamp also emits a wide band of wavelengths other than 222 nm, especially UVC at a longer wavelength than 222 nm and ultraviolet B, which cause DNA damage. There are some reports on the critical role of bandpass filters in reducing the harmful effect of UVC emitted from a KrCl excimer lamp in a human skin model and human subjects. However, the effectiveness of a bandpass filter has not been demonstrated in animal experiments. In the present study, mice were irradiated with UVC emitted from a KrCl excimer lamp with or without a bandpass filter. UVC emitted from an unfiltered KrCl lamp at doses of 50, 150 and 300 mJ/cm2 induced cyclobutyl pyrimidine dimer (CPD)-positive cells, whereas UVC emitted from a filtered lamp did not significantly increase CPD-positive cells in the epidermis. The present study suggested that the bandpass filter serves a critical role in reducing the harmful effect of emission outside of 222 nm to mouse keratinocytes.

High-pressure crystallography shows noble gas intervention into protein-lipid interaction and suggests a model for anaesthetic action.

In this work we examine how small hydrophobic molecules such as inert gases interact with membrane proteins (MPs) at a molecular level. High pressure atmospheres of argon and krypton were used to produce noble gas derivatives of crystals of three well studied MPs (two different proton pumps and a sodium light-driven ion pump). The structures obtained using X-ray crystallography showed that the vast majority of argon and krypton binding sites were located on the outer hydrophobic surface of the MPs - a surface usually accommodating hydrophobic chains of annular lipids (which are known structural and functional determinants for MPs). In conformity with these results, supplementary in silico molecular dynamics (MD) analysis predicted even greater numbers of argon and krypton binding positions on MP surface within the bilayer. These results indicate a potential importance of such interactions, particularly as related to the phenomenon of noble gas-induced anaesthesia.

Deep-mantle krypton reveals Earth's early accretion of carbonaceous matter.

Establishing when, and from where, carbon, nitrogen and water were delivered to Earth is a fundamental objective in understanding the origin of habitable planets such as Earth. Yet, volatile delivery to Earth remains controversial1-5. Krypton isotopes provide insights on volatile delivery owing to their substantial isotopic variations among sources6-10, although pervasive atmospheric contamination has hampered analytical efforts. Here we present the full suite of krypton isotopes from the deep mantle of the Galápagos and Iceland plumes, which have the most primitive helium, neon and tungsten isotopic compositions11-16. Except for 86Kr, the krypton isotopic compositions are similar to a mixture of chondritic and atmospheric krypton. These results suggest early accretion of carbonaceous material by proto-Earth and rule out any combination of hydrodynamic loss with outgassing of the deep or shallow mantle to explain atmospheric noble gases. Unexpectedly, the deep-mantle sources have a deficit in the neutron-rich 86Kr relative to the average composition of carbonaceous meteorites, which suggests a nucleosynthetic anomaly. Although the relative depletion of neutron-rich isotopes on Earth compared with carbonaceous meteorites has been documented for a range of refractory elements1,17,18, our observations suggest such a depletion for a volatile element. This finding indicates that accretion of volatile and refractory elements occurred simultaneously, with krypton recording concomitant accretion of non-solar volatiles from more than one type of material, possibly including outer Solar System planetesimals.

Xenon Trapping in Metal-Supported Silica Nanocages.

Xenon (Xe) is a valuable and scarce noble gas used in various applications, including lighting, electronics, and anesthetics, among many others. It is also a volatile byproduct of the nuclear fission of uranium. A novel material architecture consisting of silicate nanocages in contact with a metal surface and an approach for trapping single Xe atoms in these cages is presented. The trapping is done at low Xe pressures and temperatures between 400 and 600 K, and the process is monitored in situ using synchrotron-based ambient pressure X-ray photoelectron spectroscopy. Release of the Xe from the cages occurs only when heating to temperatures above 750 K. A model that explains the experimental trapping kinetics is proposed and tested using Monte Carlo methods. Density functional theory calculations show activation energies for Xe exiting the cages consistent with experiments. This work can have significant implications in various fields, including Xe production, nuclear power, nuclear waste remediation, and nonproliferation of nuclear weapons. The results are also expected to apply to argon, krypton, and radon, opening an even more comprehensive range of applications.

Thermodynamic exploration of xenon/krypton separation based on a high-throughput screening.

Nanoporous framework materials are a promising class of materials for energy-efficient technology of xenon/krypton separation by physisorption. Many studies on Xe/Kr separation by adsorption have focused on the determination of structure/property relationships, the description of theoretical limits of performance, and the identification of top-performing materials. Here, we provide a study based on a high-throughput screening of the adsorption of Xe, Kr, and Xe/Kr mixtures in 12 020 experimental MOF materials, to provide a better comprehension of the thermodynamics behind Xe/Kr separation in nanoporous materials and the microscopic origins of Xe/Kr selectivity at both low and ambient pressure.

Computer Modeling Indicates Dramatically Less DNA Damage from Far-UVC Krypton Chloride Lamps (222 nm) than from Sunlight Exposure.

This study aims to investigate, with computer modeling, the DNA damage (assessed by cyclobutane pyrimidine dimer (CPD) formation) from far-ultraviolet C (far-UVC) in comparison with sunlight exposure in both a temperate (Harwell, England) and Mediterranean (Thessaloniki, Greece) climate. The research utilizes the published results from Barnard et al. [Barnard, I.R.M (2020) Photodermatol. Photoimmunol. Photomed. 36, 476-477] to determine the relative CPD yield of unfiltered and filtered far-UVC and sunlight exposure. Under current American Conference of Governmental Industrial Hygienists (ACGIH) exposure limits, 10 min of sunlight at an ultraviolet (UV) Index of 4-typical throughout the day in a temperate climate from Spring to Autumn-produces equivalent numbers of CPD as 700 h of unfiltered far-UVC or more than 30 000 h of filtered far-UVC at the basal layer. At the top of the epidermis, these values are reduced to 30 and 300 h, respectively. In terms of DNA damage induction, as assessed by CPD formation, the risk from sunlight exposure greatly exceeds the risk from far-UVC. However, the photochemistry that will occur in the stratum corneum from absorption of the vast majority of the high-energy far-UVC photons is unknown, as are the consequences.

Fabrication of pH-Responsive Polyimide Polyacrylic Acid Smart Gating Membranes: Ultrafast Method Using 248 nm Krypton Fluoride Excimer Laser.

pH-responsive smart gating membranes were developed using a two-step fabricating process. In the first step, a porous polyimide (PI) support membrane with ordered, regular, and well-defined pores was obtained with a 248 nm KrF excimer laser using a lithography technique. The porous membranes were then grafted with poly(acrylic acid) (PAAc) hydrogel by free radical polymerization using the same excimer laser. The number of pulses and frequency could be varied to obtain a range of water permeabilities. Permeability of membrane changed significantly due to swelling and deswelling of PAAc inside the pores at pH 7 and pH 3, respectively. These hydrogel networks were firmly grafted inside pores and remained mechanically intact even after using high pressure during permeability studies. PAAc grafting was confirmed using ATR-FTIR. PAAc hydrogel distribution inside membrane pores was analyzed using SEM and fluorescence microscopy. To quantify the amount of polymer grafted, TGA studies were carried out. Diffusion studies were also carried out using caffeine as a drug molecule to evaluate the application of membrane in drug delivery devices. The linear drug release profile obtained from the study confirmed the potential application of membrane for drug delivery purposes. Results obtained also suggest that the fabrication method developed is fast, efficient, solvent-free, and economical.

Exposure of Human Skin Models to KrCl Excimer Lamps: The Impact of Optical Filtering†.

Far-UVC radiation is a promising technology that is potentially both effective at killing airborne microbes such as coronaviruses and influenza, and being minimally hazardous to the skin and eyes. Our previous studies on health risks from far-UVC have employed a krypton-chloride (KrCl) excimer lamp, emitting principally at 222 nm, supplemented with an optical filter to remove longer wavelength emissions inherent to these lamps. This study explores KrCl lamp health hazards by comparing filtered and unfiltered KrCl lamps using effective spectral irradiance calculations and experimental skin exposures. Analysis of effective irradiances showed a notable increase in allowable exposure when using a filter. Induction of DNA dimers (CPD and 6-4PP) was measured in human skin models exposed to a range of radiant exposures up to 500 mJ cm-2 . Compared to sham-exposed tissues, the unfiltered KrCl lamps induced a statistically significant increase in the yield of both DNA lesions at all the radiant exposures studied. Conversely, filtered KrCl lamps do not induce increased levels of dimers at the current daily TLV exposure limit for 222 nm (23 mJ cm-2 ). This work supports the use of filters for far-UVC KrCl excimer lamps when used to limit disease transmission in occupied locations.

Comparison of 81mKrypton and 99mTc-Technegas for ventilation single-photon emission computed tomography in severe chronic obstructive pulmonary disease.

INTRODUCTION: Ventilation and perfusion single-photon emission computed tomography combined with computed tomography (SPECT/CT) is a powerful tool to assess the state of the lungs in chronic obstructive pulmonary disease (COPD). 81mKrypton is a gaseous ventilation tracer and distributes similarly to air, but is not widely available and relatively expensive. 99mTc-Technegas is cheaper and has wider availability, but is an aerosol, which may deposit in hot spots as the severity of COPD increases. In this study, 81mKrypton and 99mTc-Technegas were compared quantitatively in patients with severe COPD. METHODS: The penetration ratio, the heterogeneity index (with and without band filtering for relevant clinical sizes) and hot spot appearance were assessed in eleven patients with severe COPD that underwent simultaneous dual-isotope ventilation SPECT/CT with both 99mTc-Technegas and 81mKrypton. RESULTS: Significant differences were found in the penetration ratio for the medium energy general purpose (MEGP) collimators, but not for the low energy general purpose (LEGP) collimators. The difference in the overall and the band filtered heterogeneity index was significant in most cases. All patients suffered from 99mTc-Technegas hot spots in at least one lung. Comparison of MEGP 81mKrypton and LEGP Technegas scans revealed similar results as the comparison for the MEGP collimators. CONCLUSION: Caution should be taken when replacing 81mKrypton with 99mTc-Technegas as a ventilation tracer in patients with severe COPD as there are significant differences in the distribution of the tracers over the lungs. Furthermore, this patient group is prone to 99mTc-Technegas hot spots and might need additional scanning if hot spots severely hamper image interpretation.

Krypton-derivatization highlights O2-channeling in a four-electron reducing oxidase.

F420H2-oxidase (FprA) catalyses the four-electron reduction of O2 to 2H2O using the reduced form of F420 as electron donor. The hydrophobic O2-channel detected by Kr-derivatization and the concerted movement of a gating loop could contribute to prevent unwanted side-reaction between the catalytic intermediates and solvents, therefore preventing reactive oxygen species formation.

Exploring the gas access routes in a [NiFeSe] hydrogenase using crystals pressurized with krypton and oxygen.

Hydrogenases are metalloenzymes that catalyse both H2 evolution and uptake. They are gas-processing enzymes with deeply buried active sites, so the gases diffuse through channels that connect the active site to the protein surface. The [NiFeSe] hydrogenases are a special class of hydrogenases containing a selenocysteine as a nickel ligand; they are more catalytically active and less O2-sensitive than standard [NiFe] hydrogenases. Characterisation of the channel system of hydrogenases is important to understand how the inhibitor oxygen reaches the active site to cause oxidative damage. To this end, crystals of Desulfovibrio vulgaris Hildenborough [NiFeSe] hydrogenase were pressurized with krypton and oxygen, and a method for tracking labile O2 molecules was developed, for mapping a hydrophobic channel system similar to that of the [NiFe] enzymes as the major route for gas diffusion.