Comparing levoglucosan and mannosan ratios in sediments and corresponding aerosols from recent Australian fires.

The monosaccharide anhydrides levoglucosan, mannosan, and galactosan are known as 'fire sugars' as they are powerful proxies used to trace fire events. Despite their increasing use, their application is not completely understood, especially in the context of tracing past fire events using sediment samples. There are many uncertainties about fire sugar formation, partitioning, transport, complexation, and stability along all stages of the source-to-sink pathway. While these uncertainties exist, the efficacy of fire sugars as fire tracers remains limited. This study compared high-resolution fire sugar fluxes in freshwater sediment cores to known fire records in Tasmania, Australia. Past fire events correlated with fire sugar flux increases down-core, with the magnitude of the flux inversely proportional to the distance of the fires from the study site. For the first time, fire sugar ratios (levoglucosan/mannosan, L/M) in aerosols were compared with those in sediments from the same time-period. The L/M ratio in surface sediments (1.42-2.58) were significantly lower than in corresponding aerosols (5.08-15.62). We propose two hypotheses that may explain the lower average L/M of sediments. Firstly, the degradation rate of levoglucosan is higher than mannosan in the water column, sediment-water interface, and/or sediment. Secondly, the L/M ratio of non-atmospheric emissions during fires may be lower than that of atmospheric emissions from the same fire. Due to the uncertainties about transport partitioning (atmospheric versus non-atmospheric emissions) and fire sugar degradation along all stages of the source-to-sink pathway, we advise caution when inferring vegetation type (e.g. softwood, hardwood, or grasses) based purely on fire sugar ratios in sediments (e.g. L/M ratio). Future investigations are required to increase the efficacy of fire sugars as a complimentary, or standalone, fire tracer in sediments.

Accelerator mass spectrometry measurements of 233U in groundwater, soil and vegetation at a legacy radioactive waste site.

Low-level radioactive wastes were disposed at the Little Forest Legacy Site (LFLS) near Sydney, Australia between 1960 and 1968. According to the disposal records, 233U contributes a significant portion of the inventory of actinide activity buried in the LFLS trenches. Although the presence of 233U in environmental samples from LFLS has been previously inferred from alpha-spectrometry measurements, it has been difficult to quantify because the 233U and 234U α-peaks are superimposed. Therefore, the amounts of 233U in groundwaters, soils and vegetation from the vicinity of the LFLS were measured using accelerator mass spectrometry (AMS). The AMS results show the presence of 233U in numerous environmental samples, particularly those obtained within, and in the immediate vicinity of, the trenched area. There is evidence for dispersion of 233U in groundwater (possibly mobilised by co-disposed organic liquids), and the data also suggest other sources of 233U contamination in addition to the trench wastes. These may include leakages and spills from waste drums as well as waste burnings, which also occurred at the site. The AMS results confirm the historic information regarding disposal of 233U in the LFLS trenches. The AMS technique has been valuable to ascertain the distribution and environmental behaviour of 233U at the LFLS and the results demonstrate the applicability of AMS for evaluating contamination of 233U at other radioactive waste sites.

A record of fallout 239Pu and 240Pu at World Heritage Bathurst Harbour, Tasmania, Australia.

This study presents the first measurements of anthropogenic plutonium (239Pu and 240Pu) concentrations and atom ratios (240Pu/239Pu) for Tasmania, in sediment collected from Bathurst Harbour, in the Tasmanian Wilderness World Heritage Area, Australia. The weighted mean 240Pu/239Pu atom ratio measured at this site was 0.172 ± 0.007 which is consistent with published data from mainland Australia and global and Southern Hemisphere averages. The 240Pu/239Pu atom ratios ranged between 0.11 and 0.21 with the earliest recorded 240Pu/239Pu atom ratios being the lowest, suggesting an influence of low atom ratio fallout from nuclear testing in Australia. Post-moratorium fallout 240Pu/239Pu atom ratios were consistent with other records. Lead-210 (210Pb) sediment chronologies indicate sediment accumulation rates have increased since the early part of the 19th century at this location.

Differentiating Fukushima and Nagasaki plutonium from global fallout using 241Pu/239Pu atom ratios: Pu vs. Cs uptake and dose to biota.

Plutonium (Pu) has been released in Japan by two very different types of nuclear events - the 2011 Fukushima accident and the 1945 detonation of a Pu-core weapon at Nagasaki. Here we report on the use of Accelerator Mass Spectrometry (AMS) methods to distinguish the FDNPP-accident and Nagasaki-detonation Pu from worldwide fallout in soils and biota. The FDNPP-Pu was distinct in local environmental samples through the use of highly sensitive 241Pu/239Pu atom ratios. In contrast, other typically-used Pu measures (240Pu/239Pu atom ratios, activity concentrations) did not distinguish the FDNPP Pu from background in most 2016 environmental samples. Results indicate the accident contributed new Pu of ~0.4%-2% in the 0-5 cm soils, ~0.3%-3% in earthworms, and ~1%-10% in wild boar near the FDNPP. The uptake of Pu in the boar appears to be relatively uninfluenced by the glassy particle forms of fallout near the FDNPP, whereas the 134,137Cs uptake appears to be highly influenced. Near Nagasaki, the lasting legacy of Pu is greater with high percentages of Pu sourced from the 1945 detonation (~93% soils, ~88% earthworm, ~96% boar). The Pu at Nagasaki contrasts with that from the FDNPP in having proportionately higher 239Pu and was distinguished by both 240Pu/239Pu and 241Pu/239Pu atom ratios. However, compared with the contamination near the Chernobyl accident site, the Pu amounts at all study sites in Japan are orders of magnitude lower. The dose rates from Pu to organisms in the FDNPP and Nagasaki areas, as well as to human consumers of wild boar meat, have been only slightly elevated above background. Our data demonstrate the greater sensitivity of 241Pu/239Pu atom ratios in tracing Pu from nuclear releases and suggest that the Nagasaki-detonation Pu will be distinguishable in the environment for much longer than the FDNPP-accident Pu.

Radionuclides in sea turtles at the Montebello Islands former nuclear test sites: Current and historical dose rates for adults and embryos.

Radionuclides from 1950s weapons testing at the Montebello Islands, Western Australia, may impact sea turtle embryos incubating within eggs laid in contaminated sands or be taken up into adult body tissues where they can contribute to radiation dose over a turtles' 60+ year lifespan. We measured plutonium in all local samples including turtle skin, bones, hatchlings, eggshells, sea sediments, diet items and beach sands. The amount of Pu in developing embryos/hatchling samples was orders of magnitude lower than that in the surrounding sands. These contaminated sands caused most dose to eggs (external dose from 137Cs, 152Eu), while most of the dose to adults was from internalised radionuclides (98%). While current dose rates are relatively low, local dose rates were high for about ten years following the 1950s detonations and may have resulted in lethality or health impacts to a generation of turtles that likely carry biomarkers today.

Challenges associated with the behaviour of radioactive particles in the environment.

A series of different nuclear sources associated with the nuclear weapon and fuel cycles have contributed to the release of radioactive particles to the environment. Following nuclear weapon tests, safety tests, conventional destruction of weapons, reactor explosions and fires, a major fraction of released refractory radionuclides such as uranium (U) and plutonium (Pu) were present as entities ranging from sub microns to fragments. Furthermore, radioactive particles and colloids have been released from reprocessing facilities and civil reactors, from radioactive waste dumped at sea, and from NORM sites. Thus, whenever refractory radionuclides are released to the environment following nuclear events, radioactive particles should be expected. Results from many years of research have shown that particle characteristics such as elemental composition depend on the source, while characteristics such as particle size distribution, structure, and oxidation state influencing ecosystem transfer depend also on the release scenarios. When radioactive particles are deposited in the environment, weathering processes occur and associated radionuclides are subsequently mobilized, changing the apparent Kd. Thus, particles retained in soils or sediments are unevenly distributed, and dissolution of radionuclides from particles may be partial. For areas affected by particle contamination, the inventories can therefore be underestimated, and impact and risk assessments may suffer from unacceptable large uncertainties if radioactive particles are ignored. To integrate radioactive particles into environmental impact assessments, key challenges include the linking of particle characteristics to specific sources, to ecosystem transfer, and to uptake and retention in biological systems. To elucidate these issues, the EC-funded COMET and RATE projects and the IAEA Coordinated Research Program on particles have revisited selected contaminated sites and archive samples. This COMET position paper summarizes new knowledge on key sources that have contributed to particle releases, including particle characteristics based on advanced techniques, with emphasis on particle weathering processes as well as on heterogeneities in biological samples to evaluate potential uptake and retention of radioactive particles.

Modeling and validation of uniform large-area optical coating deposition on a rotating drum using microwave plasma reactive sputtering.

Magnetron sputter deposition onto a rotating drum is a method applied to high-throughput large-area optical coating deposition, where film physical thickness uniformity is an important parameter. Techniques have been developed, such as masking/substrate movement, in order to improve sputtered film uniformity. In this study, a model is described and validated for predicting film uniformity. Experimental data show excellent agreement with modeled simulations, with and without a modified sputtering mask. Practical application is demonstrated in maximizing uniformity over an individual substrate size of 100 cm2 for a high-optical-density visible/near-infrared dual-band laser protection filter.

Measurement of (233)U/(234)U ratios in contaminated groundwater using alpha spectrometry.

The uranium isotope (233)U is not usually observed in alpha spectra from environmental samples due to its low natural and fallout abundance. It may be present in samples from sites in the vicinity of nuclear operations such as reactors or fuel reprocessing facilities, radioactive waste disposal sites or sites affected by clandestine nuclear operations. On an alpha spectrum, the two most abundant alpha emissions of (233)U (4.784 MeV, 13.2%; and 4.824 MeV, 84.3%) will overlap with the (234)U doublet peak (4.722 MeV, 28.4%; and 4.775 MeV, 71.4%), if present, resulting in a combined (233+234)U multiplet. A technique for quantifying both (233)U and (234)U from alpha spectra was investigated. A series of groundwater samples were measured both by accelerator mass spectrometry (AMS) to determine (233)U/(234)U atom and activity ratios and by alpha spectrometry in order to establish a reliable (233)U estimation technique using alpha spectra. The Genie™ 2000 Alpha Analysis and Interactive Peak Fitting (IPF) software packages were used and it was found that IPF with identification of three peaks ((234)U minor, combined (234)U major and (233)U minor, and (233)U major) followed by interference correction on the combined peak and a weighted average activity calculation gave satisfactory agreement with the AMS data across the (233)U/(234)U activity ratio range (0.1-20) and (233)U activity range (2-300 mBq) investigated. Correlation between the AMS (233)U and alpha spectrometry (233)U was r(2) = 0.996 (n = 10).

In-situ microfluidic controlled, low temperature hydrothermal growth of nanoflakes for dye-sensitized solar cells.

In this paper, an in-situ microfluidic control unit (MCU) was designed and applied in a hydrothermal synthesis process, which provides an easy way to localize liquid-phase reaction and realize selective synthesis and direct growth of nanostructures as well as their morphology, all in a low-temperature and atmospheric environment. The morphology was controlled through controlling the amount of additivities using the MCU. This achieved a facile fabrication of Al doped ZnO (AZO) nanoflakes vertically grown on flexible polymer substrates with enhanced light scattering and dye loading capabilities. Flexible DSSCs with a significant enhancement (410% compare to ZnO NRs based devices) in power conversion efficiency were obtained using AZO nanoflake photoanodes of 6 µm thick, due to the enhancement in electron mobility and reduction in recombination. This hydrothermal synthesis using the in-situ MCU provides an efficient and scalable technique to synthesize controllable nanostructures with characteristics of easy set-up, low energy consumption and low cost.

Birth defects and anti-heat shock protein 70 antibodies in early pregnancy.

Abstract It has been suggested that induction of the heat shock response in the mammalian embryo during the critical period of organogenesis can result in anatomical malformation. We measured serum heat shock protein 70 (Hsp70), anti-Hsp70, and anti-Hsp60 in samples taken from expectant mothers at 16 weeks gestation. Samples from women whose babies were born with a birth defect (n = 30) were compared with controls who gave birth to healthy babies (n = 46). Anti-Hsp70 levels were significantly elevated in patients who later gave birth to babies with cleft lip or palate or neurological abnormalities (n = 10): 260 (223-406) microg/mL compared to 150 (88-207) microg/mL in controls (P < 0.001). No significant differences were found in serum Hsp70 and anti-Hsp60 levels between cases and controls. This finding of increased maternal anti-Hsp70 in patients who later gave birth to babies with these abnormalities suggests a previous stressful event may have contributed to the pathogenesis. Further work is required to determine whether Hsp70 has a direct or indirect role in this pathogenesis or whether anti-Hsp70 is simply a marker of a prior increase in Hsp70 due to a physiological stress that itself resulted in the damage. This work is consistent with previous studies showing a buffering role for Hsps in evolution.

Folate supplementation reduces serum hsp70 levels in patients with type 2 diabetes.

Type 2 diabetes patients are subject to oxidative stress as a result of hyperglycemia. The aim of this study was to determine whether administration of the antioxidant folic acid, previously shown to reduce homocysteine levels, would reduce circulating levels of Hsp70 while improving the condition of type 2 diabetes patients with microalbuminuria. Plasma homocysteine fell from pretreatment values of 12.9 to 10.3 microM (P < 0.0001). The urine albumin-creatinine ratio fell from 12.4 to 10.4 mg/mM (P = 0.38). Pretreatment Hsp70 levels were higher in patients not taking insulin (5.32 ng/mL) compared with those on insulin (2.44 ng/mL) (P = 0.012). Folic acid supplementation resulted in a significant fall in Hsp70 (5.32 to 2.05 ng/mL) (P = 0.004). There was no change in Hsp70 in those receiving insulin. Folic acid supplementation in non-insulin-treated type 2 diabetes patients, therefore, resulted in a fall in Hsp70, reflecting an improvement in oxidative stress. The data shows that improvement in homocysteine status can lead to a reduction in Hsp70, indicating the possibility of its use as a marker for severity of disease.