Multiphoton Phosphorescence of Simple Ketones by Visible-light Excitation and Its Consideration for Active Sensing in Space.

Acetone and butanone were seen to emit blue light around 450 nm when excited in the green by a high intensity pulsed laser. The pathway of this anti-Stokes emission is believed to be multiphoton absorption followed by phosphorescence, with emission being observed in the samples at cryogenic temperatures below their melting point and not seen from either ketone in their cold liquid state. Given the widespread nature of these simple ketones in off-world bodies and their potential importance as an organic resource for Space Resource Utilization, signals which enable the identification and tracing of these materials are of use in applications from remote sensing and mapping to monitoring during extraction processes. While the excitation process has a low efficiency, the ability to use visible light for sensing of these targets has advantages over UV sources, such as the wider availability of high-powered lasers which could be utilized.

SEARCH FOR EXPERIMENTAL EVIDENCE OF DOSE-RATE AND WALL SCATTERING EFFECTS IN THE THERMOLUMINESCENCE RESPONSE OF LIF:MG,TI (TLD-100).

An experimental investigation into the possibility of dose-rate effects and wall scatter in the thermoluminescent response of LiF:Mg,Ti (TLD-100) was carried out. The investigation was motivated by theoretical simulations predicting the possible presence of dose-rate effects coupled with the lack of detailed experimental studies. The dose rate was varied by changing the source to sample distance, by the use of attenuators, sources of 137Cs of various activities, filtration and the construction of identical geometrical irradiators of Teflon and stainless steel. Four levels of dose in the linear dose response region were studied at 10-2 Gy, 1.5 × 10-2 Gy, 0.1 Gy and 0.5 Gy to avoid complications in interpretation due to supralinearity above 1 Gy. At the dose of 1.5 × 10-2 Gy, the dose rate was varied by five orders of magnitude from 4.9 × 10-3 Gy s-1 to 4.9 × 10-8 Gy s-1. At the other levels of dose, a one to two orders of magnitude in dose rate was achieved. Within the measurement uncertainty of 5-10%, no dose-rate effects were observed in any of the experimental measurements and no changes in the shape of the glow curve were observed. The maximum wall scatter effect (Teflon to stainless steel) was measured at ~8% within the experimental uncertainty and well below expectations. The results are encouraging with respect to the accurate and reproducible use of LiF:Mg,Ti under various experimental conditions of irradiation.

Selective radionuclide co-sorption onto natural minerals in environmental and anthropogenic conditions.

Anthropogenic activities can redistribute the constituents of naturally occurring radioactive materials (NORM), posing potential hazards to populations and ecosystems. In the present study, the co-sorption of several RN from the U decay chain- 238U, 230Th, 226Ra, 210Pb and 210Po, onto common minerals associated with mining activities (chalcopyrite, bornite, pyrite and barite) was investigated, in order to identify the various factors that control long-term NORM mobility and retentivity in environmental acid-mine drainage systems and hydrometallurgical processing. The results show selective RN co-sorption to the various natural minerals, suggesting that mineral-specific mechanisms govern the variability in NORM mobility and retentivity. Both 226Ra and 210Po underwent significant sorption onto the natural minerals investigated in this study. The order of co-sorption in sulfate media for chalcopyrite and bornite was 210Po>226Ra>206Pb>210Pb>238U/230Th. Conversely, both pyrite and barite showed increased affinity for 226Ra; the order of co-sorption in sulfate media was 226Ra>210Po>206Pb/210Pb>238U/230Th for pyrite and 226Ra>206Pb/210Pb>230Th/238U/210Po for barite. Similar orders of co-sorption were observed in the nitrate media: for chalcopyrite and bornite the order was 210Po>226Ra/206Pb/210Pb/238U/230Th compared to 226Ra>210Po/206Pb/210Pb/238U/230Th for pyrite and barite. The behavior of 210Po was found to the anomalous: in both sulfate and nitrate solutions, 210Po had little affinity for barite compared to the sulfides. Thermodynamic modeling indicated the formation of a reduced PoS(s) phase at the surface of sulfide minerals, leading to the suggestion that 210Po likely undergoes reductive precipitation on the surface of sulfide minerals. The high sorption of both 206Pb and 210Pb observed in the sulfate systems were likely as a result of co-precipitation as insoluble anglesite compared to nitrate where they mainly remained in solution. Overall, barite showed the highest affinity for 226Ra, given its propensity to sorb 226Ra (similar ionic size). Both 238U and 230Th were highly mobile in acidic sulfate and nitrate solutions. The results highlighted here identify the various constraints on the natural variability and fractionation of NORM in the environment, as well as the mineral-specific mechanisms that control co-sorption of RN. This information provides a framework for predicting RN transport within soils and ground waters with variable geochemical conditions and in metallurgical extraction processes, in order to develop effective strategies towards NORM mitigation.

Upconversion Fluorescence in Naturally Occurring Calcium Fluoride.

Fluorine can negatively interfere with leach and smelting processes during mineral processing. Real-time knowledge of the concentration and mineral hosts of fluorine in a mineral processing ore stream is important to protect process line equipment and product. Currently only offline methods of detection are available. Online sensors that determine specific fluorine-bearing mineral concentration in real-time would enable improved efficiency in processing decisions during mine production. Common excitation wavelengths used for fluorescence studies in minerals frequently provide signals that are not clearly host-specific, and hence of limited utility for mineral identification. We show that upconversion fluorescence, a process in which two or more photons are absorbed and one higher-energy photon is emitted, provides a more host-specific fluorescence output, minimizing spurious signals in complex environments and therefore greatly improving detection thresholds. Natural samples of fluorite (CaF2), a major fluorine host at many mine sites, have been analyzed by near-infrared excitation and have revealed upconversion fluorescence from rare earth inclusions. Upconversion fluorescence was detected in samples with rare earth concentrations as low as one part per million and is therefore considered a potential new sensing modality for real-time fluorite monitoring.

Quantification of radionuclide distribution and migration during Cu-(Fe)-sulphide mineral processing by alpha particle autoradiography.

Understanding the movement of radionuclides (RNs) between different mineral hosts during processing of base metal ores is critical for accurate modelling of RN deportment and optimisation of processes designed to reduce or eliminate RNs. Here, we demonstrate that spatially resolving quantitative alpha particle autoradiography combined with backscatter electron imaging and energy dispersive X-ray spectroscopy (EDS) can establish the correlation between alpha-emitting RNs (notably 226Ra and 210Po, daughters of the abundant 238U decay series) and certain minerals, in different stages of processing. This is achieved by locating the RNs to a specific mineral grain, the species of which can subsequently be identified using EDS. The mineralogy of RN-associated grains can then be compared with the mineral suite and relative abundances of the species within the sample, by relating how often each mineral is associated with alpha decay-events. In the processing of uranium-bearing copper ores, migration of alpha-emitting RN daughters of the 238U series were observed, and these RNs were demonstrated to correlate strongly with barite, bornite and covellite over other coexisting minerals.

Understanding the mobility and retention of uranium and its daughter products.

Knowledge of the behavior of technologically enhanced naturally occurring radioactive materials derived through the decay of U and its daughter products, and their subsequent fractionation, mobilization and retention, is essential to develop effective mitigation strategies and long-term radiological risk prediction. In the present study, multiple state-of-the-art, spatially resolved micro-analytical characterization techniques were combined to systematically track the liberation and migration of radionuclides (RN) from U-bearing phases in an Olympic Dam Cu flotation concentrate following sulfuric-acid-leach processing. The results highlighted the progressive dissolution of U-bearing minerals (mainly uraninite) leading to the release, disequilibrium and ultimately upgrade of daughter RN from the parent U. This occurred in conjunction with primary Cu-Fe-sulfide minerals undergoing coupled-dissolution reprecipitation to the porous secondary Cu-mineral, covellite. The budget of RN remaining in the leached concentrate was split between RN still hosted in the original U-bearing minerals, and RN that were mobilized and subsequently sorbed/precipitated onto porous covellite and auxiliary gangue mineral phases (e.g. barite). Further grinding of the flotation concentrate prior to sulfuric-acid-leach led to dissolution of U-bearing minerals previously encapsulated within Cu-Fe-sulfide minerals, resulting in increased release and disequilibrium of daughter RN, and causing further RN upgrade. The various processes that affect RN (mobility, sorption, precipitation) and sulfide minerals (coupled-dissolution reprecipitation and associated porosity generation) occur continuously within the hydrometallurgical circuit, and their interplay controls the rapid and highly localized enrichment of RN. The innovative combination of tools developed here reveal the heterogeneous distribution and fractionation of the RN in the ores following hydrometallurgical treatment at nm to cm-scales in exquisite detail. This approach provides an effective blueprint for understanding of the mobility and retention of U and its daughter products in complex anthropogenic and natural processes in the mining and energy industries.

Publisher Correction: First experimental evaluation of the alpha efficiency in coarse-grained quartz for ESR dating purposes: implications for dose rate evaluation.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

First experimental evaluation of the alpha efficiency in coarse-grained quartz for ESR dating purposes: implications for dose rate evaluation.

We present the first experimental evaluation of the alpha efficiency value for electron spin resonance (ESR) dating of coarse quartz grains, which is used for the evaluation of the internal and external alpha dose rate components. Based on our results, we recommend the use of an a-value of 0.07 ± 0.01 (1σ) for both the Al and Ti centres. Although we acknowledge that quartz ESR alpha efficiency may be sample dependent, and could also be impacted by other sources of uncertainty, this potential variability is presently impossible to evaluate given the absence of other experimental a-values available in the ESR dating literature. Measured radioactivity of quartz grains from the Moulouya catchment (NE Morocco) provides an internal dose rate in the range of 50-70 µGy/a when using an a-value of 0.07. The use of this empirically derived a-value for the evaluation of the internal and external alpha dose rate has a limited overall impact on the final ESR age results: they change by <2% and <3%, respectively, in comparison with those obtained with an assumed a-value. However, the large variability observed among the broader sample dataset for quartz internal radioactivity and hydrofluoric acid (HF) etching rates underscores the potential importance of undertaking experimental evaluations of alpha dose rate parameters for each dated sample.

Somewhere beyond the sea: Human cranial remains from the Lesser Sunda Islands (Alor Island, Indonesia) provide insights on Late Pleistocene peopling of Island Southeast Asia.

The migration of anatomically modern humans (AMH) from Africa to every inhabitable continent included their dispersal through Island Southeast Asia (ISEA) to Australia. Significantly, this involved overwater dispersal through the Lesser Sunda Islands between Sunda (continental Southeast Asia) and Sahul (Australia and New Guinea). However, the timing and direction of this movement is still debated. Here, we report on human skeletal material recovered from excavations at two rockshelters, known locally as Tron Bon Lei, on Alor Island, Indonesia. The remains, dated to the Late Pleistocene, are the first anatomically modern human remains recovered in Wallacea dated to this period and are associated with cultural material demonstrating intentional burial. The human remains from Tron Bon Lei represent a population osteometrically distinct from Late Pleistocene Sunda and Sahul AMH. Instead, morphometrically, they appear more similar to Holocene populations in the Lesser Sundas. Thus, they may represent the remains of a population originally from Sunda whose Lesser Sunda Island descendants survived into the Holocene.

Rapid and automated production of [68Ga]gallium chloride and [68Ga]Ga-DOTA-TATE on a medical cyclotron.

INTRODUCTION: The demand for Gallium-68 (68Ga) for labelling PET radiopharmaceuticals has increased over the past few years. 68Ga is obtained through the decayed parent radionuclide 68Ge using commercial 68Ge/68Ga generators. The principal limitation of commercial 68Ge/68Ga generators is that only a limited and finite quantity of 68Ga (<1.85 GBq at start of synthesis) may be accessed. The focus of this study was to investigate the use of a low energy medical cyclotron for the production of greater quantities of 68Ga and to develop an automated and rapid procedure for processing the product. METHODS: Enriched ZnCl2 was electrodeposited on a platinum backing using a NH4Cl (pH 2-4) buffer. The Zn target was irradiated with GE PETtrace 880 at 35 µA and 14.5 and 12.0 MeV beam energy. The irradiated Zn target was purified using octanol resin on an automated system. RESULTS: Following the described procedure, 68Ga was obtained in 6.30 ±â€¯0.42 GBq after 8.5 min bombardment and with low radionuclidic impurities (66Ga (<0.005%) and 67Ga (<0.09%)). Purification on a single octanol resin gave 82% recovery with resulting [68Ga]GaCl3 obtained in 3.5 mL of 0.2 M HCl. [68Ga]GaCl3 production from irradiation to final product was <45 min. To highlight the utility of the automated procedure, [68Ga]Ga-DOTA-TATE labelling was incorporated to give 1.56 GBq at EOS of the labelled peptide with RCY of >70%. CONCLUSIONS: A straightforward procedure for producing 68Ga on a low energy medical cyclotron was described. Current efforts are focus on high activity production and radiolabelling using solid target produced 68Ga.

Alpha particle autoradiography for high spatial resolution mapping of radionuclides.

An autoradiographic technique capable of determining the spatial location of radioactive isotopes within materials on the scale of micrometers is demonstrated in low-activity mineral samples, where the concentrations of radionuclides with short half lives is small and below the detection limits of current measurement techniques. The location of certain radionuclide species within samples with complex structures on the micron scale can yield valuable information, however current methods do not have the spatial resolution required for this purpose. We demonstrate the use of an autoradiographic emulsion to directly image alpha particle events in samples with low radionuclide concentrations, allowing spatial resolution of radionuclide locations on the order of several microns. Exposure over a long time period allows sufficient integration of decay events enabling analysis of samples with low activity but large area, (less than 1×10-4 Bq/mm2). The use of polarising filters to increase contrast between the alpha particle tracks and the substrate during imaging demonstrates the viability of the technique on samples with a complex structure.

When did Homo sapiens first reach Southeast Asia and Sahul?

Anatomically modern humans (Homo sapiens, AMH) began spreading across Eurasia from Africa and adjacent Southwest Asia about 50,000-55,000 years ago (ca 50-55 ka). Some have argued that human genetic, fossil, and archaeological data indicate one or more prior dispersals, possibly as early as 120 ka. A recently reported age estimate of 65 ka for Madjedbebe, an archaeological site in northern Sahul (Pleistocene Australia-New Guinea), if correct, offers what might be the strongest support yet presented for a pre-55-ka African AMH exodus. We review evidence for AMH arrival on an arc spanning South China through Sahul and then evaluate data from Madjedbebe. We find that an age estimate of >50 ka for this site is unlikely to be valid. While AMH may have moved far beyond Africa well before 50-55 ka, data from the region of interest offered in support of this idea are not compelling.

Versatile PbS Quantum Dot Ligand Exchange Systems in the Presence of Pb-Thiolates.

A robust solution phase ligand exchange system for lead sulfide (PbS) quantum dots (QDs) in the presence of Pb-thiolate ligands is presented that can better preserve the excitonic absorption and emission features as compared to the conventional ligands. The photoluminescence after ligand exchange of PbS QDs with Pb-thiolate ligand is preserved up to 78% of the original oleate capped PbS QDs.

Cultural innovation and megafauna interaction in the early settlement of arid Australia.

Elucidating the material culture of early people in arid Australia and the nature of their environmental interactions is essential for understanding the adaptability of populations and the potential causes of megafaunal extinctions 50-40 thousand years ago (ka). Humans colonized the continent by 50 ka, but an apparent lack of cultural innovations compared to people in Europe and Africa has been deemed a barrier to early settlement in the extensive arid zone. Here we present evidence from Warratyi rock shelter in the southern interior that shows that humans occupied arid Australia by around 49 ka, 10 thousand years (kyr) earlier than previously reported. The site preserves the only reliably dated, stratified evidence of extinct Australian megafauna, including the giant marsupial Diprotodon optatum, alongside artefacts more than 46 kyr old. We also report on the earliest-known use of ochre in Australia and Southeast Asia (at or before 49-46 ka), gypsum pigment (40-33 ka), bone tools (40-38 ka), hafted tools (38-35 ka), and backed artefacts (30-24 ka), each up to 10 kyr older than any other known occurrence. Thus, our evidence shows that people not only settled in the arid interior within a few millennia of entering the continent, but also developed key technologies much earlier than previously recorded for Australia and Southeast Asia.

Mechanistic insight into the nucleation and growth of oleic acid capped lead sulphide quantum dots.

The quantum dots (QDs) of lead sulphide (PbS) are attractive near-infrared (NIR) active materials and have promising applications in a wide variety of applications. Till date many efforts have been made on optimizing its synthesis; however, current mechanistic understanding involving the nucleation and growth of these QDs has not reached the same level as that for other QDs. In this study, we present a detailed understanding on synthesis mechanism of PbS QDs so as to provide guidance for future QDs synthesis. The synthesis of PbS QDs is largely independent of classical nucleation process and the hot-injection of precursors may not be necessary for the successful synthesis of PbS QDs. The synthesis is basically a growth dominated process and is controlled by the Ostwald ripening of PbS QDs. In addition, reaction temperature and ligand are the key parameters for controlling QD growth. Temperature provides energy for overcoming activation barrier of QD growth while the ligands enhance QD growth via altering the environment for QD growth. Following the mechanism governing the synthesis of PbS QDs, we demonstrate that the size tuning of PbS QDs in ultra-small (<2 nm) can be achieved, which has been typically challenging following the hot injection synthesis.

Human predation contributed to the extinction of the Australian megafaunal bird Genyornis newtoni ∼47 ka.

Although the temporal overlap between human dispersal across Australia and the disappearance of its largest animals is well established, the lack of unambiguous evidence for human-megafauna interactions has led some to question a human role in megafaunal extinction. Here we show that diagnostic burn patterns on eggshell fragments of the megafaunal bird Genyornis newtoni, found at >200 sites across Australia, were created by humans discarding eggshell in and around transient fires, presumably made to cook the eggs. Dating by three methods restricts their occurrence to between 53.9 and 43.4 ka, and likely before 47 ka. Dromaius (emu) eggshell occur frequently in deposits from >100 ka to present; burnt Dromaius eggshell first appear in deposits the same age as those with burnt Genyornis eggshell, and then continually to modern time. Harvesting of their eggs by humans would have decreased Genyornis reproductive success, contributing to the bird's extinction by ∼47 ka.

Identification and quantification of explosives in nanolitre solution volumes by Raman spectroscopy in suspended core optical fibers.

A novel approach for identifying explosive species is reported, using Raman spectroscopy in suspended core optical fibers. Numerical simulations are presented that predict the strength of the observed signal as a function of fiber geometry, with the calculated trends verified experimentally and used to optimize the sensors. This technique is used to identify hydrogen peroxide in water solutions at volumes less than 60 nL and to quantify microgram amounts of material using the solvent's Raman signature as an internal calibration standard. The same system, without further modifications, is also used to detect 1,4-dinitrobenzene, a model molecule for nitrobenzene-based explosives such as 2,4,6-trinitrotoluene (TNT).

Stratigraphy and chronology of the WLH 50 human remains, Willandra Lakes World Heritage Area, Australia.

We present a detailed description of the geological setting of the burial site of the WLH 50 human remains along with attempts to constrain the age of this important human fossil. Freshwater shells collected at the surface of Unit 3, which is most closely associated with the human remains, and a carbonate sample that encrusted the human bone were analysed. Gamma spectrometry was carried out on the WLH 50 calvaria and TIMS U-series analysis on a small post-cranial bone fragment. OSL dating was applied to a sample from Unit 3 at a level from which the WLH 50 remains may have eroded, as well as from the underlying sediments. Considering the geochemistry of the samples analysed, as well as the possibility of reworking or burial from younger layers, the age of the WLH 50 remains lies between 12.2 ± 1.8 and 32.8 ± 4.6 ka (2-σ errors).

New ages for human occupation and climatic change at Lake Mungo, Australia.

Australia's oldest human remains, found at Lake Mungo, include the world's oldest ritual ochre burial (Mungo III) and the first recorded cremation (Mungo I). Until now, the importance of these finds has been constrained by limited chronologies and palaeoenvironmental information. Mungo III, the source of the world's oldest human mitochondrial DNA, has been variously estimated at 30 thousand years (kyr) old, 42-45 kyr old and 62 +/- 6 kyr old, while radiocarbon estimates placed the Mungo I cremation near 20-26 kyr ago. Here we report a new series of 25 optical ages showing that both burials occurred at 40 +/- 2 kyr ago and that humans were present at Lake Mungo by 50-46 kyr ago, synchronously with, or soon after, initial occupation of northern and western Australia. Stratigraphic evidence indicates fluctuations between lake-full and drier conditions from 50 to 40 kyr ago, simultaneously with increased dust deposition, human arrival and continent-wide extinction of the megafauna. This was followed by sustained aridity between 40 and 30 kyr ago. This new chronology corrects previous estimates for human burials at this important site and provides a new picture of Homo sapiens adapting to deteriorating climate in the world's driest inhabited continent.