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Recent research has shown the potential of speleothem δ13C to record a range of environmental processes. Here, we report on 230Th-dated stalagmite δ13C records for southwest Sulawesi, Indonesia, over the last 40,000 yr to investigate the relationship between tropical vegetation productivity and atmospheric methane concentrations. We demonstrate that the Sulawesi stalagmite δ13C record is driven by changes in vegetation productivity and soil respiration and explore the link between soil respiration and tropical methane emissions using HadCM3 and the Sheffield Dynamic Global Vegetation Model. The model indicates that changes in soil respiration are primarily driven by changes in temperature and CO2, in line with our interpretation of stalagmite δ13C. In turn, modelled methane emissions are driven by soil respiration, providing a mechanism that links methane to stalagmite δ13C. This relationship is particularly strong during the last glaciation, indicating a key role for the tropics in controlling atmospheric methane when emissions from high-latitude boreal wetlands were suppressed. With further investigation, the link between δ13C in stalagmites and tropical methane could provide a low-latitude proxy complementary to polar ice core records to improve our understanding of the glacial–interglacial methane budget. [ABSTRACT FROM AUTHOR]

The determination of inorganic anions in uranium ore concentrates (UOCs) is useful to nuclear forensics for establishing the provenance of sample materials. In this collaborative study, quantitation of inorganic anions was carried out on three UOC reference materials from the National Research Council Canada: UCLO-1 (https://doi.org/10.4224/crm.2020.uclo-1), UCHI-1 (https://doi.org/10.4224/crm.2020.uchi-1), and UPER-1 (https://doi.org/10.4224/crm.2020.uper-1). The analytes were extracted into water and characterized by ion chromatography with combined standard uncertainties (uc) between 1.6 and 11%. The highest contributor to uc was homogeneity. Sulfate was the most abundant anion (2000–12,000 mg/kg SO42−). Other anions were in the 15–500 mg/kg range. [ABSTRACT FROM AUTHOR]

The University of Wollongong (UOW) cosmogenic 10Be and 26Al sample preparation laboratory has been in operation since the start of 2017. As primarily a feeder laboratory to ANSTO's Centre for Accelerator Science, our sample preparation procedures have been optimised with consideration to the setup of ANSTO's 6MV SIRIUS accelerator, and aim to achieve a balance between sample throughput as well as Be and Al target purity. A comparatively small number of samples (n = 68) have also been prepared for measurement at the Australian National University 14UD accelerator. 10Be/9Be ratios of procedural blanks measured on SIRIUS have fluctuated over time with the median for the year 2017 being 5.16 × 10−16 (IQR = 4.11 × 10−16 to 7.16 × 10−16, n = 18), increasing to 1.62 × 10−15 (IQR = 1.05 × 10−15 to 2.17 × 10−15, n = 31) for 2018 and 2019, a period coinciding with elevated boron levels in our samples, and finally decreasing to 1.15 × 10−15 (IQR = 8.63 × 10−16 to 1.60 × 10−15, n = 34) for 2020 and 2021. In contrast, 26Al/27Al ratios of procedural blanks measured on SIRIUS have shown a slight but continuous improvement over time with the median for 2017 of 1.70 × 10−15 (IQR = 8.19 × 10−16 to 5.25 × 10−15, n = 12) decreasing to 1.07 × 10−15 (IQR = 8.5 × 10−16 to 1.53 × 10−15, n = 13) for 2021. Median 10Be/9Be relative uncertainty of procedural blanks analysed on SIRIUS is 18 % (IQR = 15 % to 22 %; n = 86) whereas the median 26Al/27Al relative uncertainty of procedural blanks is higher at 60 % (IQR = 41 % to 100 %; n = 56), statistic resulting from most blanks yielding low 26Al counts (median = 2; IQR = 1–4.5). Average 9BeO− output relative to standard is between ∼ 70 % – 80 % for samples analysed on SIRIUS (n = 895) and ∼ 130 % for samples analysed at ANU (n = 68). 27Al− output relative to standard is lower for samples pressed into cathodes at UOW (∼60 %, n = 432) and analysed on SIRIUS than for those pressed at ANSTO (∼90 %, n = 119). Average 27Al− output relative to standard for samples analysed at ANU is ∼ 80 % (n = 62). 10Be and 26Al measurements of various laboratory intercomparison materials prepared at UOW between 2017 and 2022 yield results in agreement with consensus values confirming that our chemistry procedures are robust and in line with those elsewhere. [ABSTRACT FROM AUTHOR]

Geochemical proxies and diatom assemblages were used in combination with grain size characteristics not only to describe the deposit left behind by the 27 February 2010, Maule tsunami at Las Cañas, Maule Region, Chile, but also to trace the maximum inundation limit of the event. The sandy deposit was laid down between 160 and 260 m inland behind an eroded sand dune and a lagoon but reached only 60% of the total tsunami inundation distance of 380 m, which was marked by organic debris, pumice clasts and wooden logs. It consisted of coarse to medium sand that thinned and fined inland. At the most seaward point, the 22 cm thick deposit exhibited a fining upward unit overlain by a couplet of coarsening–fining upward units, suggesting deposition by at least two waves, while farther inland the fining upward deposit was probably left behind by only one wave. Chemical proxies (Ca/Ti vs Sr/Ba) allow us to distinguish the deposit from the surrounding soil and indicate that it was sourced from the beach and/or dune area, with diatom assemblages confirming the marine origin of the deposit. Saltwater indicators (e.g. Cl, S) provide evidence for the maximum inundation limit beyond the extent of the sandy deposit, despite dilution and dissolution by 500 mm of rainfall in the six months since the tsunami. Marine and marine/brackish diatom assemblages decreased landward but were found up to the inundation limit and immediately beyond, suggesting the effect of diatom-bearing sea spray at the wave front or redistribution of the detrital assemblage associated with tsunami inundation due to wind. While the latter might result in a slight over-estimation of the inundation distance, they can be used in combination with chemical proxies to trace the maximum inundation distance of recent and past tsunamis, thus allowing for a better estimation of the magnitude of past events. Post-depositional processes were found to have affected the thinner sandy deposits (< 5 cm), suggesting that these are unlikely to be preserved in the geological record. This highlights the need to be able to trace the tsunami inundation limit with geochemical and/or diatom proxies without having to rely on sedimentological evidence, as it is now widely recognised that conventional approaches used by tsunami researchers have led to an under-estimation of previous events. [ABSTRACT FROM AUTHOR]

Abstract: Large areas of farmland in the Sendai Plain, Japan, were inundated by the 11 March 2011 Tohoku-oki tsunami and covered by a discontinuous 30–0.2cm thick sediment layer consisting of sand and/or mud and generally thinning and fining inland. Two months after the tsunami, numerous rice paddy fields and depressions remained ponded with brackish or saline water. A series of field surveys in May, August and October 2011 were carried out north of Sendai airport, in order to assess the environmental impact of the tsunami. While evaporation had resulted in elevated conductivity in ponded water in May (up to 68.2mScm−1), rainfall over the next five months led to dilution, although brackish water was still recorded in depressions and on paddy fields. Tsunami sediments, underlying soil and soil beyond the tsunami inundation limit were collected at 43 sites along and near a transect extending over 5km inland, and analysed for grain size, organic content, water leachable ions, acid leachable metals and exchangeable metalloids. Water leachable anion and cation concentrations were elevated in sandy and muddy tsunami deposits and soils particularly in areas, where seawater had stagnated for a longer period of time after the tsunami, with up to 10.5% Cl, 6.6% Na, 2.8% SO4, 440mgkg−1 Br measured in surface sediments (<0.5cm depth). Vertical variations were also recorded, with higher concentrations often measured in the surface samples. A similar trend could be observed for some of the metalloids (As) and metals (Zn, Cu and Ni), although in general, maximum concentrations of metals and metalloids were not much higher than in soils not inundated by the tsunami and were within background levels for uncontaminated Japanese soils. The impact of saltwater inundation was documented in the chemistry of soils underlying tsunami sediments, which were affected by salt contamination down to ~15cm depth, and soils not covered by tsunami deposits. The latter implies that the extent of tsunami inundation may successfully be determined using geochemical markers in absence of any sedimentological evidence. Water leachable ions mostly decreased over time, however, they remained high enough to impact on rice farming, which was completely halted in 2011. Although further work is required to assess the longer term impact of tsunami inundation, flushing of salt with freshwater, as well as the possible removal of sandy/muddy sediments and underlying soil are recommended to allow crop production to resume. [Copyright &y& Elsevier]

Local carbonate cycling in lagoon-estuarine systems, involving processes such as inorganic and biogenic carbonate precipitation/dissolution, represents an important but poorly constrained component of the coastal carbon budget. This study investigates the sensitivity of stable Sr isotope tracer (δ88/86Sr) with respect to carbonate saturation and salinity of local waters in the Coorong, Lower Lakes and Murray Mouth (CLLMM) estuary in South Australia. The CLLMM has an extensive range of salinity from fresh to hypersaline (from ∼0 to over 100 PSU), with corresponding variations in water chemistry and major ion composition that in turn controls mineral saturation states, and thus CaCO 3 precipitation/dissolution in local waters. Here we use the novel δ88/86Sr tracer in tandem with the more established radiogenic Sr isotope ratio (87Sr/86Sr), where the latter is a robust proxy for Sr sources and thus water provenance. We also produced a geochemical (PHREEQC) model of calcium carbonate (CaCO 3) saturation changes across this unique lagoon-estuarine system. The results indicate a systematically increasing trend of δ88/86Sr (from ∼0.25‰ to ∼0.45‰) with increasing salinity and CaCO 3 (aragonite, calcite) saturation indices of the coastal waters, which in turn suggest an overall control of carbonate dissolution/precipitation processes on the stable Sr isotope composition in the CLLMM system. This was further corroborated by Ca isotope data (δ44/40Ca) published previously on the same samples from the Coorong, as well as a quantitative simulation of local carbonate removal in the lagoon based on Rayleigh modelling and Sr isotope data. Overall, our results confirm that a coupled Sr isotope approach (combining 87Sr/86Sr and δ88/86Sr) can be used to constrain not only the main water sources (continental versus marine Sr) but also local CaCO 3 dissolution/precipitation processes, and thus inorganic carbon and coastal carbonate cycling in the CLLMM system. Finally, this coupled δ88/86Sr and 87Sr/86Sr approach can be potentially applied to fossil carbonate archives to reconstruct paleo-hydrology and salinity changes in the CLLMM and/or other carbonate-producing coastal systems. [ABSTRACT FROM AUTHOR]

The trace-element geochemistry of speleothems is becoming increasingly used for reconstructing palaeoclimate, with a particular emphasis on elements whose concentrations vary according to hydrological conditions at the cave site (e.g. Mg, Sr, Ba and U). An important step in interpreting trace-element abundances is understanding the underlying processes of their incorporation. This includes quantifying the fractionation between the solution and speleothem carbonate via partition coefficients (where the partitioning (D) of element X (D X) is the molar ratio [X/Ca] in the calcite divided by the molar ratio [X/Ca] in the parent water) and evaluating the degree of spatial variability across time-constant speleothem layers. Previous studies of how these elements are incorporated into speleothems have focused primarily on stalagmites and their source waters in natural cave settings, or have used synthetic solutions under cave-analogue laboratory conditions to produce similar dripstones. However, dripstones are not the only speleothem types capable of yielding useful palaeoclimate information. In this study, we investigate the incorporation of Mg, Sr, Ba and U into a subaqueous calcite speleothem (CD3) growing in a natural cave pool in Italy. Pool-water measurements extending back 15 years reveal a remarkably stable geochemical environment owing to the deep cave setting, enabling the calculation of precise solution [X/Ca]. We determine the trace element variability of 'modern' subaqueous calcite from a drill core taken through CD3 to derive D Mg , D Sr , D Ba and D U then compare these with published cave, cave-analogue and seawater-analogue studies. The D Mg for CD3 is anomalously high (0.042 ± 0.002) compared to previous estimates at similar temperatures (∼8 °C). The D Sr (0.100 ± 0.007) is similar to previously reported values, but data from this study as well as those from Tremaine and Froelich (2013) and Day and Henderson (2013) suggest that [Na/Sr] might play an important role in Sr incorporation through the potential for Na to outcompete Sr for calcite non-lattice sites. D Ba in CD3 (0.086 ± 0.008) is similar to values derived by Day and Henderson (2013) under cave-analogue conditions, whilst D U (0.013 ± 0.002) is almost an order of magnitude lower, possibly due to the unusually slow speleothem growth rates (<1 μm a−1), which could expose the crystal surfaces to leaching of uranyl carbonate. Finally, laser-ablation ICP-MS analysis of the upper 7 μm of CD3, regarded as 'modern' for the purposes of this study, reveals considerable heterogeneity, particularly for Sr, Ba and U, which is potentially indicative of compositional zoning. This reinforces the need to conduct 2D mapping and/or multiple laser passes to capture the range of time-equivalent elemental variations prior to palaeoclimate interpretation. [ABSTRACT FROM AUTHOR]

CuI is a candidate wasteform for the immobilization of the fission product 129 I. CuI can be made simply by the addition of CuCl to an I − bearing solution such that exchange of Cl − with I − takes place. The CuI material can then be consolidated into a wasteform by sintering at approximately 550 °C in argon or by hot isostatically pressing at 550 °C with 100 MPa of pressure. A waste loading of greater than 60 wt.% is achievable with good water leach resistance, in keeping with the low solubility product of CuI. However, like the well known wasteform candidate AgI, CuI decomposes in water containing metallic Fe. To compensate this deficiency, the sintered CuI wasteform can be further protected by surrounding it by Sn powder and HIPing at the low temperature of 200 °C. [ABSTRACT FROM AUTHOR]

During the 1960s, radioactive waste containing small amounts of plutonium (Pu) and americium (Am) was disposed in shallow trenches at the Little Forest Burial Ground (LFBG), located near the southern suburbs of Sydney, Australia. Because of periodic saturation and overflowing of the former disposal trenches, Pu and Am have been transferred from the buried wastes into the surrounding surface soils. The presence of readily detected amounts of Pu and Am in the trench waters provides a unique opportunity to study their aqueous speciation under environmentally relevant conditions. This study aims to comprehensively investigate the chemical speciation of Pu and Am in the trench water by combining fluoride coprecipitation, solvent extraction, particle size fractionation, and thermochemical modeling. The predominant oxidation states of dissolved Pu and Am species were found to be Pu(IV) and Am(III), and large proportions of both actinides (Pu, 97.7%; Am, 86.8%) were associated with mobile colloids in the submicron size range. On the basis of this information, possible management options are assessed. [ABSTRACT FROM AUTHOR]

Early in 2009, a state policing agency raided a clandestine drug laboratory in a suburb of a major city in Australia. During the search of the laboratory, a small glass jar labelled ''GammaSource'' and containing a green powder was discovered. The powder was radioactive. This paper documents the detailed nuclear forensic analysis undertaken to characterise and identify the material and determine its provenance. Isotopic and impurity content, phase composition, microstructure and other characteristics were measured on the seized sample, and the results were compared with similar material obtained from the suspected source (ore and ore concentrate material). While an extensive range of parameters were measured, the key 'nuclear forensic signatures' used to identify the material were the U isotopic composition, Pb and Sr isotope ratios, and the rare earth element pattern. These measurements, in combination with statistical analysis of the elemental and isotopic content of the material against a database of uranium ore concentrates sourced from mines located worldwide, led to the conclusion that the seized material (a uranium ore concentrate of natural isotopic abundance) most likely originated from Mary Kathleen, a former Australian uranium mine. [ABSTRACT FROM AUTHOR]

Abstract: A technique for the isolation of thorium (Th), plutonium (Pu), americium (Am), uranium (U) and strontium (Sr) isotopes from various environmental matrices has been adapted from a previously published method specific to water samples (). Separation and isolation of the various elemental fractions from a single sub-sample is possible, thereby eliminating the need for multiple analyses. The technique involves sample dissolution, concentration via calcium phosphate co-precipitation, rapid column extraction using TEVA™, TRU™ and Sr-Spec™ resin cartridges, alpha spectrometry for Th, Pu, U and Am and Cerenkov counting for Sr. Various standard reference materials were analysed and chemical yields are in the range of 70–80% for Th, Am, U and Sr and 50–60% for Pu. Sample sizes of up to 10 L for water, 5 g for dry soil and sediment and 10 g for dry vegetation and seaweed can be processed using this technique. [Copyright &y& Elsevier]

Chemical toxicants, particularly metal ions, are a major contaminant in global waterways. Live-organism bioassays used to monitor chemical toxicants commonly involve measurements of activity or survival of a freshwater cladoceran (Ceriodaphnia dubia) or light emitted by the marine bacterium Vibrio fischeri, used in the commercial Microtox1 bioassay. Here we describe a novel moleculebased assay system employing DNA as the chemical biosensor. Metals bind to DNA, causing structural changes that expel a bound (intercalated) fluorescent reporter dye. Analyses of test data using 48 wastewater samples potentially contaminated by metal ions show that the DNA-dye assay results correlate with those from C. dubia and Microtox bioassays. All three assays exhibit additive, antagonistic, and synergistic responses that cannot be predicted by knowing individual metal concentrations. Analyses of metals in these samples imply the presence of chemical toxicants other than metal ions. The DNA-dye assay is robust, has a 12-month shelf life, and is only slightly affected by sample pH in the range 4 to 9. The assay is completed in a matter of minutes, and its portability makes it well suited as a screening assay for use in the field. We conclude that the DNA-dye test is a surrogate bioassay suitable for screening chemical toxicity. [ABSTRACT FROM AUTHOR]

Titanium dioxide (TiO2) has often served as a model substrate for experimental sorption studies of environmental contaminants. However, various forms of Ti-oxide have been used, and the different sorption properties of these materials have not been thoroughly studied. We investigated uranium sorption on some thoroughly characterized TiO2 surfaces with particular attention to the influence of surface area, surface charge, and impurities. The sorption of U(VI) differed significantly between samples. Aggressive pretreatment of one material to remove impurities significantly altered the isoelectric point, determined by an electroacoustic method, but did not significantly impact U sorption. Differences in sorption properties between the various TiO2 materials were related to the crystallographic form, morphology, surface area, and grain size, rather than to surface impurities or surface charge. In-situ attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopic studies showed that the spectra of the surface species of the TiO2 samples are not significantly different, suggesting the formation of similar surface complexes. The data provide insights into the effect of different source materials and surface properties on radionuclide sorption. [ABSTRACT FROM AUTHOR]

Abstract: Elemental and isotopic ratio analyses of U ore concentrate samples, from the 3 operating U mining facilities in Australia, were carried out to determine if significant variations exist between their products, thereby allowing the U ore concentrate’s origin to be identified. Elemental analyses were conducted using inductively coupled plasma mass spectrometry (ICP-MS) and X-ray fluorescence spectrometry (XRF). Lead isotope ratios were measured using ICP-MS and U isotope analyses were conducted using thermal ionisation mass spectrometry (TIMS). Minute quantities of sample, such as that obtained from a swipe, were also examined for elemental concentrations using secondary ion mass spectrometry (SIMS). The results of multivariate statistical analysis show clear patterns in the trace elemental composition of the processed U ores, indicating that it is possible to use this feature as a unique identifier of an Australian U ore concentrate’s source. Secondary ion mass spectrometry analyses also allow individual particles to be differentiated using this ‘fingerprinting’ technique. Isotope ratios determined using TIMS reveal that there is a significant difference in the n(234U)/n(238U) isotope ratio between the U ore concentrate from each mine. [Copyright &y& Elsevier]

Abstract: A thorough understanding of cave seepage waters is necessary to interpret geochemical variations in speleothem calcite in terms of changing surface climatic conditions at a particular site. Here we present the hydrochemistry of ten cave drip waters from a karst system in SE Australia based on up to 5.5 years of monitoring. Discharge was continuously measured at six sites and manually at the other sites. Dripwater samples were analysed for pH, electrical conductivity, cations and anions at all sites at monthly or more frequent intervals. Each drip possesses a unique chemistry, and not all drip waters responded to antecedent short-term hydrological variations. For example, the hydrochemical behaviour of three adjacent drips at a bedrock depth of 45 m was completely different to that of shallower sites, and was apparently un-related to surface hydrology throughout the investigation. Based on modelled calcite precipitation vectors, prior calcite precipitation was demonstrated at several sites but can only be linked directly to changes in surface recharge at the shallowest sites. At extremely low flow, shallow drip waters accessed a high Mg, Sr and Ba source, thought to be the overlying soil. High-frequency sample collection allows for the calculation of predicted Mg/Cacalcite and Sr/Cacalcite values, highlighting that the sites with the greatest potential to record high-resolution palaeohydrological records are those situated at shallow depth. Longer temporal-resolution palaeohydrological records may be recorded at deeper sites but longer-term monitoring is required to identify probable time scales. Inherent system non-linearities, dissolution of secondary calcite in pore spaces of the aquifer, changes in the source of trace elements, and the presence of multiple reservoirs confirm the need for the use of multiple speleothems and a multi-proxy approach to gain accurate palaeohydrological records from this site. [Copyright &y& Elsevier]

Three sedimentary sequences from a coastal wetland behind a sand barrier, on the west coast of d'Urville Island, New Zealand, were examined using a multi-proxy approach, including sedimentological, geochemical and microfossil (diatom) analyses, with the chronology established using radiocarbon and 210Pb dating. Data show that a brackish lagoon started developing 7300 year ago after formation of the sand barrier in Moawhitu. This was followed by periods of alternating wetland encroachment and open water, displaying spatial variations, until a peatland was established about 1300 cal. yr BP. The wetland was then partially drained in the early 1900s, leading to compaction of the peat near the surface. A coarse layer containing gravel, sand and shells, with a sharp lower contact, in the northern area of the wetland, is attributed to an overwash about 2500–3000 yr BP, most probably a tsunami generated by the rupture of a local or regional fault. The high-resolution continuous record obtained with XRF core scanning revealed a geochemical signature (Ca and S) for the overwash 600 m inland in the middle area of the wetland, while it was absent from the southern site 1.1 km from the shore. This suggests that, except at the northern end of Moawhitu, the sand dune acted as an effective barrier preventing any sediment from overtopping 2500–3000 yr BP, with only a geochemical evidence marking the extent of seawater inundation. No sedimentological or geochemical evidence could be found in the wetland for the 15th century tsunami that had destroyed almost an entire community in Moawhitu, as recounted in Māori oral tradition (pūrākau), although pebbles at the surface of the dune are likely to be linked to this event. Thus, the sand dune appears to have again acted as an effective barrier for the overwash in the 15th century. However, our study suggests that the area might have been impacted by more than one tsunami in the last 3000 years. It also shows that a high-resolution continuous XRF record can provide the evidence for short-term changes (catastrophic or not) that did not leave any clear sedimentological signature, thus providing a better insight of environmental changes in any depositional environment. [ABSTRACT FROM AUTHOR]

Abstract: Three pressed leaves of Ulmus glabra (Wych Elm) were found within the pages of a copy of the Great Bible in the Library of the University of Western Australia. The Bible dates from AD 1540 and was originally housed at Ely Cathedral in Cambridgeshire. A radiocarbon age on one of the leaves found it was about as old as the Great Bible itself, and stable C and N isotope and neutron activation analyses were carried out on the same leaf. The δ15N values were elevated and the content of iron, arsenic, bromine, silver, gold and mercury were relatively high. These analyses are consistent with an environment where water logging is present, as at Ely at the time, and the silver and gold content are probably consistent with the cathedral setting. The mercury was found to be associated with the red ink in the Bible. It is intriguing to ponder why Wych elm leaves were placed in the Bible, especially in the light that a copy of an original edition of the King James version of the Bible from Ely, also in the library in Perth has many dozens of U. glabra leaves also preserved within in its pages. [Copyright &y& Elsevier]