We combine in situ laser spectroscopy, quantum chemistry, and kinetic calculations to study the reaction of a singlet oxygen atom with dimethyl ether. Infrared laser absorption spectroscopy and Faraday rotation spectroscopy are used for the detection and quantification of the reaction products OH, H2O, HO2, and CH2O on submillisecond time scales. Fitting temporal profiles of products with simulations using an in-house reaction mechanism allows product branching to be quantified at 30, 60, and 150 Torr. The experimentally determined product branching agrees well with master equation calculations based on electronic structure data and transition state theory. The calculations demonstrate that the dimethyl peroxide (CH3OOCH3) generated via O-insertion into the C-O bond undergoes subsequent dissociation to CH3O + CH3O through energetically favored reactions without an intrinsic barrier. This O-insertion mechanism can be important for understanding the fate of biofuels leaking into the atmosphere and for plasma-based biofuel processing technologies.
Manipulating surface charge, electric field, and plasma afterglow in a non-equilibrium plasma is critical to control plasma-surface interaction for plasma catalysis and manufacturing. Here, we show enhancements of surface charge, electric field during breakdown, and afterglow by ferroelectric barrier discharge. The results show that the ferroelectrics manifest spontaneous electric polarization to increase the surface charge by two orders of magnitude compared to discharge with an alumina barrier. Time-resolved in-situ electric field measurements reveal that the fast polarization of ferroelectrics enhances the electric field during the breakdown in streamer discharge and doubles the electric field compared to the dielectric barrier discharge. Moreover, due to the existence of surface charge, the ferroelectric electrode extends the afterglow time and makes discharge sustained longer when alternating the external electric field polarity. The present results show that ferroelectric barrier discharge offers a promising technique to tune plasma properties for efficient plasma catalysis and electrified manufacturing.
Plasmas can generate ultra-high-temperature reactive environments that can be used for the synthesis and processing of a wide range of materials1,2. However, the limited volume, instability and non-uniformity of plasmas have made it challenging to scalably manufacture bulk, high-temperature materials3-8. Here we present a plasma set-up consisting of a pair of carbon-fibre-tip-enhanced electrodes that enable the generation of a uniform, ultra-high temperature and stable plasma (up to 8,000 K) at atmospheric pressure using a combination of vertically oriented long and short carbon fibres. The long carbon fibres initiate the plasma by micro-spark discharge at a low breakdown voltage, whereas the short carbon fibres coalesce the discharge into a volumetric and stable ultra-high-temperature plasma. As a proof of concept, we used this process to synthesize various extreme materials in seconds, including ultra-high-temperature ceramics (for example, hafnium carbonitride) and refractory metal alloys. Moreover, the carbon-fibre electrodes are highly flexible and can be shaped for various syntheses. This simple and practical plasma technology may help overcome the challenges in high-temperature synthesis and enable large-scale electrified plasma manufacturing powered by renewable electricity.
Acute hemorrhage in pregnancy may lead to maternal and/or fetal morbidity or mortality. In emergency medicine, blockage of the aorta via an inflatable endovascular balloon, technically referred to Resuscitative Endovascular Balloon Occlusion of the Aorta (REBOA), is used to manage hemorrhage. However, the application of REBOA in pregnancy needs to strike a balance between two competing objectives of limiting maternal blood loss and ensuring fetal wellness, for which one would need to predict the impact of regulated blood pressure on fetal wellness. To address this problem, we propose an efficient machine learning-based method to predict the temporal impact of the distal Mean Arterial Blood Pressure (dMAP) controlled by the REBOA on the oxygen content in the fetal blood. Evaluation of the algorithm on data collected from in-vivo experiments from pregnant ewe animal models exhibits mean absolute error of 0.61, 1.09, 1.42, 1.70 mmHg, and coefficient of determination of 0.95, 0.86, 0.76, 0.64 for prediction of partial pressure of oxygen in fetal arterial blood, a key predictor of fetal wellness, in 2.5, 5, 7.5, 10-minute prediction horizons, respectively.
In many low-temperature plasmas (LTPs), the OH radical and temperature represent key properties of plasma reactivity. However, OH and temperature measurements in weakly ionized LTPs are challenging, due to the low concentration and short lifetime of OH and the abrupt temperature rise caused by fast gas heating. To address such issues, this Letter combined cavity-enhanced absorption spectroscopy (CEAS) with femtosecond (fs) pulses to enable sensitive single-shot broadband measurements of OH and temperature with a time resolution of â¼180 ns in LTPs. Such a combination leveraged several benefits. With the appropriately designed cavity, an absorption gain of â¼66 was achieved, enhancing the actual OH detection limit by â¼55× to the 1011 cm-3 level (sub-ppm in this work) compared with single-pass absorption. Single-shot measurements were enabled while maintaining a time resolution of â¼180â ns, sufficiently short for detecting OH with a lifetime of â¼100 µs. With the broadband fs laser, â¼34,000 cavity modes were matched with â¼95 modes matched on each CCD pixel bandwidth, such that fs-CEAS became immune to the laser-cavity coupling noise and highly robust across the entire spectral range. Also, the broadband fs laser allowed simultaneous sensing of many absorption features to enable simultaneous multi-parameter measurements with enhanced accuracies.
Phosphorus (P) is essential for productivity of alpine grassland ecosystems, which are sensitive to global warming. We tested the hypotheses that (1) mobilized 'calcium-bound inorganic P' (Ca-Pi ) is a major source of plant-available P in alpine meadows with alkaline soils after long-term warming, (2) mobilization of Ca-Pi is linked to effective plant carboxylate-releasing P-acquisition strategies under warming, and (3) the mobilization is also related to plant nitrogen (N)-acquisition. We conducted an 8-year warming experiment in an alpine meadow (4635 m above sea level) on the Qinghai-Tibetan Plateau. A significant increase in P concentration in both aboveground and belowground biomass indicates an increased mobilization and assimilation of P by plants under warming. We observed a significant decrease in Ca-Pi , no change in moderately-labile organic P, and an increase in highly resistant organic P after warming. There was no increase in phosphatase activities. Our results indicate that Ca-Pi , rather than organic P was the major source of plant-available P for alpine meadows under warming. Higher leaf manganese concentrations of sedges and forbs after warming indicate that carboxylates released by these plants are a key mechanism of Ca-Pi mobilization. The insignificant increase in Rhizobiales after warming and the very small cover of legumes show a minor role of N-acquisition strategies in solubilizing phosphate. The insignificant change in relative abundance of mycorrhizal fungi and bacteria related to P cycling after warming shows a small contribution of microorganisms to Ca-Pi mobilization. The significant increase in leaf N and P concentrations and N:P ratio of grasses and no change in sedge leaf N:P ratio reflect distinct responses of plant nutrient status to warming due to differences in P-acquisition strategies. We highlight the important effects of belowground P-acquisition strategies, especially plant carboxylate-releasing P-acquisition strategies on responses of plants to global changes in alpine meadows.
Phosphorus , Soil , Ecosystem , Grassland , Phosphates , Tibet
Mine tailings pose physical and chemical challenges for plant establishment. Our aim was to learn from natural processes in long-term soil and ecosystem development to use tailings as novel parent materials and pioneer ecological-engineering plant species to ameliorate extreme conditions of tailings, and facilitate the establishment of subsequent native plants. A glasshouse trial was conducted using magnetite tailings containing various amendments, investigating the potential of the nitrogen (N)-fixing, non-native pioneer species Lupinus angustifolius (Fabaceae), narrow-leaf lupin, as a potential eco-engineer to promote soil formation processes, and whether amendment type or the presence of pioneer vegetation improved the subsequent establishment and growth of 40 species of native plants. We found that L. angustifolius eco-engineered the mine tailings, by enhancing the N status of tailings and mobilising primary mineral P into organic P via a carboxylate-exudation strategy, thereby enabling subsequent growth of native species. The substantial increases of the soil organic P (from ca. 10 to 150 mg kg-1) pool and organo-bound Al minerals (from 0 to 2 mg kg-1) were particularly evident, indicating the initiation of pedogenesis in mine tailings. Our findings suggest that the annual legume L. angustifolius has eco-engineering potential on mine tailings through N-fixation and P-mobilisation, promoting the subsequent growth of native plants. We proposed Daviesia (Fabaceae) species as native species alternatives for the non-native L. angustifolius in the Western Australian context. Our findings are important for restoration practitioners tasked with mine site restoration in terms of screening pioneer eco-engineering plant species, where native plants are required to restore after mine operations.
Lupinus , Soil Pollutants , Australia , Ecosystem , Ferrosoferric Oxide , Plant Leaves/chemistry , Soil , Soil Pollutants/analysis
Faraday rotation spectroscopy (FRS) employs the Faraday effect to detect Zeeman splitting in the presence of a magnetic field. In this article, we present system design and implementation of radical sensing in a photolysis reactor using FRS. High sensitivity (100 ppb) and time resolved in situ HO2 detection is enabled with a digitally balanced acquisition scheme. Specific advantages of employing FRS for sensing in such dynamic environments are examined and rigorously compared to the more established conventional laser absorption spectroscopy (LAS). Experimental results show that FRS enables HO2 detection when LAS is deficient, and FRS compares favorably in terms of precision when LAS is applicable. The immunity of FRS to spectral interferences such as absorption of hydrocarbons and other diamagnetic species absorption and optical fringing are highlighted in comparison to LAS.
BACKGROUND AND AIMS: Rates of tailings production and deposition around the world have increased markedly in recent decades, and have grown asynchronously with safe and environmentally suitable solutions for their storage. Tailings are often produced in regions harbouring biodiverse native plant communities adapted to old, highly-weathered soils. The highly-altered edaphic conditions of tailings compared with natural soils in these areas will likely select against many locally endemic plant species, making phytostabilisation, rehabilitation or ecological restoration of these landforms challenging. METHODS: We established four substrate cover composition treatments on a dry-stacked magnetite tailings storage facility in semi-arid Western Australia, representative of standard industry practices for rehabilitating or restoring post-mining landforms in the region. Plots were seeded with a selection of locally native plant species and monitored for five years to determine whether different substrate cover treatments yielded different edaphic conditions (soil moisture, substrate surface temperature and substrate chemistry) and influenced soil development and the success of native vegetation establishment. RESULTS: No vegetation established from seeds on unamended tailings with no surface cover, and substrate chemistry changed minimally over five years. In contrast, rock-containing surface covers allowed establishment of up to 11 native plant species from broadcast seeds at densities of ca. 1.5 seedlings m-2, and up to 3.5 seedlings m-2 of five native pioneer chenopods from capture of wind-dispersed seeds from surrounding undisturbed native vegetation. Greater vegetation establishment in rock-containing surface covers resulted from increased heterogeneity (e.g., lower maximum soil temperature, greater water capture and retention, surface microtopography facilitating seed capture and retention, more niches for seed germination). Soil development and bio-weathering occurred most rapidly under the canopy of native pioneer plants on rock-containing surface covers, particularly increases in organic carbon, total nitrogen, and organo-bound aluminium and iron. CONCLUSIONS: Seed germination and seedling survival on tailings were limited by extreme thermal and hydrological conditions and a highly-altered biogeochemical environment. The design of surface cover layers appears crucial to achieving closure outcomes on tailings landforms, and designs should prioritise increasing surface heterogeneity through the incorporation of rock or other structure-improving amendments to assist the establishment of pioneer vegetation.
Soil Pollutants , Soil , Mining , Plants , Soil Pollutants/analysis , Western Australia
Tailings are among the most challenging mined substrates for plant re-establishment, in particular because of a lack of soil-like structure and nitrogen. Potential pioneer plants are sometimes found in such disturbed and infertile sites. We present a group of pioneer species from the genus Maireana (Chenopodiaceae) that are promising candidates for the restoration of magnetite tailings. We found that these Maireana species did not rely on biologically fixed N from the atmosphere, but exhibited an exceptionally high leaf N-resorption efficiency (about 95%) during leaf senescence, at the same time effectively scavenging trace amount of N from the substrate, in part through rapid transpiration.
Chenopodiaceae , Soil Pollutants , Mining , Nitrogen , Soil , Soil Pollutants/analysis
Photoacoustic imaging has shown its great potential in biomedical imaging. A variety of imaging applications, like blood oxygenation for functional imaging, have been widely studied during the past few decades. Most of the previous works are based on the tissue's endogenous or nanoprobe's extraneous optical absorbance. In this paper, we proposed frequency-domain dual-contrast photoacoustic imaging aiming at exploring both optical absorption and mechanical property (e.g., viscoelasticity) of tissue. Instead of conventionally used pulsed excitation, a chirp-modulated laser signal is used to excite the sample to induce photoacoustic signals. On one hand, the optical absorption contrast is obtained by cross-correlating the PA signals with the chirp pattern. On the other hand, mechanical property is obtained by performing the Fourier transform to analyze the frequency spectrum. Experimental results revealed that samples with higher density-to-viscoelasticity ratio show larger quality factor in the received PA signals' spectrum. Both theoretical analysis and experimental demonstrations are performed to prove the feasibility of the proposed method.
Photoacoustic Techniques , Diagnostic Tests, Routine , Lasers , Light , Spectrum Analysis
Ant Forest, a mobile app developed by the monolithic Alibaba Group, is greening individuals' daily activities and transforming human capacity to reverse global environmental degradation. Over 500 million e-trees are being cultivated every day in China using Ant Forest, and over 122 million real trees have been planted over more than 112 000 ha of degraded land. Ant Forest showcases how internet technology innovation combined with digital financing and philanthropy is contributing to solving environmental issues while attracting and retaining customer loyalty. This powerful business model has the potential to spread to all manner of environmental outcomes.
Planets , Trees , China , Ecosystem , Forests , Humans
Photoacoustic imaging (PAI), an emerging imaging technique, exploits the merits of both optical and ultrasound imaging, equipped with optical contrast and deep penetration. Typical linear PAI relies on a nanosecond laser pulse to induce photoacoustic signals. To construct a multi-wavelength PAI system, a multi-wavelength nano-second laser source is required, which greatly increases the cost of the PAI system. However, according to the nonlinear photoacoustic effect, the amplitude of the photoacoustic signals will vary with different base temperatures of the tissue. Therefore, using continuous-wave lasers with different wavelengths to induce different temperature variations at the same point of the tissue, and then using a single-wavelength pulsed laser to induce photoacoustic signals has been an alternative method to achieve multi-wavelength PAI. In this paper, based on the nonlinear photoacoustic effect, we developed a continuous-wave multi-wavelength laser source to cut down the cost of the conventional multi-wavelength PAI system. The principle will be introduced firstly, followed by qualitative and quantitative experiments.
Lasers , Photoacoustic Techniques/instrumentation , Equipment Design , Nonlinear Dynamics , Phantoms, Imaging
Endemism and rarity have long intrigued scientists. We focused on a rare endemic and critically-endangered species in a global biodiversity hotspot, Grevillea thelemanniana (Proteaceae). We carried out plant and soil analyses of four Proteaceae, including G. thelemanniana, and combined these with glasshouse studies. The analyses related to hydrology and plant water relations as well as soil nutrient concentrations and plant nutrition, with an emphasis on sodium (Na) and calcium (Ca). The local hydrology and matching plant traits related to water relations partially accounted for the distribution of the four Proteaceae. What determined the rarity of G. thelemanniana, however, was its accumulation of Ca. Despite much higher total Ca concentrations in the leaves of the rare G. thelemanniana than in the common Proteaceae, very few Ca crystals were detected in epidermal or mesophyll cells. Instead of crystals, G. thelemanniana epidermal cell vacuoles contained exceptionally high concentrations of noncrystalline Ca. Calcium ameliorated the negative effects of Na on the very salt-sensitive G. thelemanniana. Most importantly, G. thelemanniana required high concentrations of Ca to balance a massively accumulated feeding-deterrent carboxylate, trans-aconitate. This is the first example of a calcicole species accumulating and using Ca to balance accumulation of an antimetabolite.
Proteaceae , Calcium , Mesophyll Cells , Plant Leaves , Soil
Photoacoustic imaging has attracted increasing research interest in recent years, due to its unique merit of combining light and sound. Enabling deep tissue imaging with high ultrasound spatial resolution and optical absorption contrast, photoacoustic imaging has been applied in various application scenarios including anatomical, functional and molecular imaging. However, the bulky and expensive laser source is one of the key bottlenecks that needs to be addressed for further compact system development. A photoacoustic imaging system based on a low-cost laser diode (LD) is one of the promising solutions. In this paper, we report a custom-made fingertip laser diode system enabling both pulsed and continuous modulation modes with shortest pulse-width of 40 ns, largest driving current of 13 A, and highest modulation frequency of 3 MHz, which is suitable for both time and frequency domain photoacoustic imaging. To the best of our knowledge, this may be the most compact laser source reported for photoacoustic imaging enabling both two modulation modes. Owing to its super-compact size, the proposed LD system could pave the pathway to a low-cost photoacoustic sensing and imaging device, even wearable photoacoustic biomedical sensors.
Diagnostic Imaging/methods , Lasers, Semiconductor , Photoacoustic Techniques/instrumentation , Equipment Design , Microscopy/methods , Molecular Imaging , Spectrum Analysis
The present study aimed to characterize key physico-chemical and mineralogical attributes of magnetite iron (Fe) ore tailings to identify potential constraints limiting in situ soil formation and direct phytostabilization. Tailings of different age, together with undisturbed local native soils, were sampled from a magnetite mine in Western Australia. Tailings were extremely alkaline (pHâ¯>â¯9.0), with a lack of water stable aggregate and organic matter, and contained abundant primary minerals including mica (e.g., biotite), with low specific surface area (N2-BET around 1.2â¯m2â¯g-1). These conditions remained relatively unchanged after four years' aging under field conditions. Chemical extraction and spectroscopic analysis [e.g., X-ray diffraction (XRD) and synchrotron-based Fe K edge X-ray absorption fine structure spectroscopy (XAFS) analysis] revealed that the aging process decreased biotite-like minerals, but increased hematite and magnetite in the tailings. However, the aged tailings lacked goethite, a compound abundant in natural soils. Examination using backscattered-scanning electron microscope - energy dispersive X-ray spectrometry (BSE-SEM-EDS) revealed that aged tailings contained discrete sharp edged Fe-bearing minerals that did not physically integrate with other minerals (e.g., Si/Al bearing minerals). In contrast, Fe minerals in native soils appeared randomly distributed and closely amassed with Si/Al rich phyllosilicates, with highly eroded edges. The lack of labile organic matter and the persistence of alkaline-saline conditions may have significantly hindered the bioweathering of Fe-minerals and the biogenic formation of secondary Fe-minerals in tailings. However, there is signature that a native pioneer plant, Maireana brevifolia can facilitate the bioweathering of Fe-bearing minerals in tailings. We propose that eco-engineering inputs like organic carbon accumulation, together with the introduction of functional microbes and pioneer plants, should be adopted to accelerate bioweathering of Fe-bearing minerals as a priority for initiating in situ soil formation in the Fe ore tailings.
Photoacoustic imaging has been intensively studied in recent years, and many of the achievements have already been applied in important biomedical and clinical applications, e.g. spectroscopic photoacoustic imaging to extract functional and molecular information. However, spectroscopic photoacoustic imaging requires expensive and bulky tunable laser source, which severely hinder its further development towards portable device. In this paper, we propose a novel imaging method, named optical spectroscopic ultrasound displacement (OSUD) imaging, which enables optical spectroscopic imaging in deep scattering tissue using multiple low-cost continuous-wave laser sources and ultrasound imaging equipment. The principle of the OSUD imaging method will be introduced, and followed by preliminary experimental results. The OSUD imaging may provide another pathway to provide spectroscopic optical absorption contrast in deep scattering tissue beyond commonly used photoacoustic imaging.
Photoacoustic Techniques , Ultrasonography , Lasers , Optical Imaging , Spectrum Analysis
Photoacoustic (PA) tomography enables imaging of optical absorption property in deep scattering tissue by listening to the PA wave. However, it is an open challenge that the conversion efficiency from light to sound based on PA effect is extremely low. The consequence is the poor signal-to-noise ratio (SNR) of PA signal especially in scenarios of low laser power and deep penetration. The conventional way to improve PA signal's SNR is data averaging, which however severely limits the imaging speed. In this paper, we propose a new adaptive wavelet threshold de-noising (aWTD) algorithm, and apply it in photoacoustic tomography to increase the PA signal's SNR without sacrificing the signal fidelity and imaging speed. PA image quality in terms of contrast is also significantly improved. The proposed method provides the potential to develop real-time low-cost PA tomography system with low-power laser source.
Algorithms , Tomography, X-Ray Computed , Signal-To-Noise Ratio
Multi-wavelength photoacoustic (PA) imaging has been studied extensively to explore the spectroscopic absorption contrast of biological tissues. To generate strong PA signals, a high-power wavelength-tunable pulsed laser source has to be employed, which is bulky and quite expensive. In this paper, we propose a hybrid multi-wavelength PA imaging (hPAI) method based on combination of single-wavelength pulsed and multi-wavelength continuous-wave (CW) laser sources. By carefully controlling laser illumination sequence (pulse-CW-pulse), and extracting the PA signals' difference before and after heating of CW lasers, the optical absorption property of multi-wavelength CW lasers could be obtained. Compared with conventional PA imaging, the proposed hPAI shows much lower system cost due to the usage of single-wavelength pulsed laser and cheap CW lasers. Theoretical analysis and analytical model are presented in this paper, followed by proof-of-concept experimental results.
Photoacoustic Techniques , Acoustics , Lasers , Multimodal Imaging , Spectrum Analysis
