Estimating the relative contributions of bedrock geology, mineralisation and anthropogenic contamination to the chemistry of samples collected at the Earth’s surface is critical in research and application fields as diverse as environmental impact studies and regional mineral exploration programs. The element lead (Pb) is a particularly useful tracer in this context, representing a toxin of environmental concern and associated with many other anthropogenic contaminants (e.g. mine wastes, waters, paints, aerosols), as well as with mineralisation. Although Pb concentration data are frequently collected in geochemical studies, isotopic analysis offers an important advantage, allowing discrimination between different sources of Pb. The Pb isotopic composition of regolith is likely to reflect contributions from underlying rock (including Pb-rich mineralisation), wind-blown dust and possibly anthropogenic sources (industry, transport, agriculture, residential, waste handling). Regolith samples collected at different depths may show distinct compositions; bedrock isotopic signatures are expected to dominate in deeper soils, whilst airborne dust and anthropogenic signatures are more important at the surface. Pb isotope ratios in the continental crust show large variations, which will be transferred to the regolith, providing a potentially unique bedrock signal that is easily measured. This research program examines if soil Pb isotope mapping can identify the underlying geology and metallogenic provinces, if different sampling and analytical approaches produce very different results, and how anthropogenic signals vary across the continent. Here, we present our results for the Northern Territory, where single regolith samples from many (not all) catchments define apparently consistent isotopic domains that can be interpreted in relation to the underlying geology (crystalline basement, basins) and mineral deposits. <b>Citation:</b> Desem, C.U., Maas, R., Woodhead, J., Carr, G. and de Caritat P., 2020. Towards a Pb isotope regolith map of the Australian continent: a Northern Territory perspective. In: Czarnota, K., Roach, I., Abbott, S., Haynes, M., Kositcin, N., Ray, A. and Slatter, E. (eds.) Exploring for the Future: Extended Abstracts, Geoscience Australia, Canberra, 1–4.

<p>Australia has a significant number of surface sediment geochemical surveys that have been undertaken by industry and government during the past 50 years. These surveys represent a vast investment, but up to now have been used in isolation from one another. The key to maximising the full potential of these data and the information they provide for mineral exploration, environmental management and agricultural purposes is using all surveys together, seamlessly. These geochemical surveys have not only sampled various landscape elements but have used multiple analytical techniques, instrumentation and laboratories. The geochemical data from these surveys need to be levelled to eliminate, as much as possible, non-geological variation. Using a variety of methodologies, including reanalysis of both international standards and small subsets of samples from previous surveys, we have created a seamless surface geochemical map for northern Australia, from nine surveys with 15605 samples. We tested our approach using two surveys from the southern Thomson Orogen, which removed interlaboratory and other analytical variation. Creation of the new combined and levelled northern Australian dataset paves the way for the application of statistical techniques, such as principal component analysis and machine learning, which maximise the value of these legacy data holdings. The methodology documented here can be applied to additional geochemical datasets that become available. <p><b>Citation:</b> Main, P. T. and Champion, D. C., 2020. Geochemistry of the North Australian Craton: piecing it together. In: Czarnota, K., Roach, I., Abbott, S., Haynes, M., Kositcin, N., Ray, A. and Slatter, E. (eds.) Exploring for the Future: Extended Abstracts, Geoscience Australia, Canberra, 1–4.

The National Geochemical Survey of Australia (NGSA) provides an internally consistent, state-of-the-art, continental-scale geochemical dataset that can be used to assess areas of Australia more elevated in commodity metals and/or pathfinder elements than others. But do regions elevated in such elements correspond to known mineralized provinces, and what is the best method for detecting and thus potentially predicting those? Here, using base metal associations as an example, I compare a trivariate rank-based index and a multivariate-based Principal Component Analysis method. The analysis suggests that the simpler rank-based index better discriminates catchments endowed with known base metal mineralization from barren ones and could be used as a first-pass prospectivity tool. <b>Citation:</b> Patrice de Caritat, Continental-scale geochemical surveys and mineral prospectivity: Comparison of a trivariate and a multivariate approach, <i>Journal of Geochemical Exploration</i>, Volume 188, 2018, Pages 87-94, ISSN 0375-6742, https://doi.org/10.1016/j.gexplo.2018.01.014

Multi-element near-surface geochemistry from the National Geochemical Survey of Australia has been evaluated in the context of mapping the exposed to deeply buried major crustal blocks of the Australian continent. The major crustal blocks, derived from geophysical and geological data, reflect distinct tectonic domains comprised of igneous, metamorphic and sedimentary rock assemblages representing a time scale ranging from early Archean to recent Cenozoic. The geochemical data have been treated as compositional data to uniquely describe and characterize the geochemistry of the major crustal blocks across Australia according to the following workflow: imputation of missing/censored data, log-ratio transformation, multivariate statistical analysis, classification/allocation, and multivariate geospatial (minimum/maximum autocorrelation factor) analysis. Using cross validation techniques the uniqueness of each major crustal block has been quantified. The abilities to predict (1) the membership, or lack thereof, of a surface regolith sample to one, or none, of the major crustal blocks, and (2) the major crustal block at sites that have not been sampled are demonstrated. In conclusion, the surface regolith of the Australian continent contains a geochemical record of the original crustal block composition, despite secondary modifications due to physical transport and chemical weathering effects. <b>Citation:</b> E.C. Grunsky, P. de Caritat, U.A. Mueller, Using surface regolith geochemistry to map the major crustal blocks of the Australian continent, <i>Gondwana Research</i>, Volume 46, 2017, Pages 227-239, ISSN 1342-937X, https://doi.org/10.1016/j.gr.2017.02.011

During the National Geochemical Survey of Australia over 1300 top and bottom sediment samples (including ~10% field duplicates) were collected from the outlet of 1186 catchments covering 81% of the continent at an average sample density of 1 site/5200 km2. The <2 mm fraction of these samples was analysed for 59 elements by ICP-MS following an aqua regia extraction. Results are used here to establish the geochemical background variation of these elements, including potentially toxic elements (PTEs), in Australian surface soil. Different methods of obtaining threshold values, which differentiate between background and those samples with unusually high element concentrations and requiring attention, are presented and compared to Western Australia's 'ecological investigation levels' (EILs) established for 14 PTEs. For Mn and V these EILs are so low that an unrealistically large proportion (~24%) of the sampled sites would need investigation in Australia. For the 12 remaining elements (As, Ba, Cd, Co, Cr, Cu, Hg, Mo, Ni, Pb, Sn and Zn) very few sample sites require investigation and most are far removed from human activity centres, potentially highlighting minor local contamination or mineral exploration potential rather than pollution. No major diffuse source of contamination by PTEs visibly affects Australian soils at the continental scale. Of the statistical methods used to establish threshold values, the most pertinent results come from identifying breaks in cumulative probability diagrams, the Tukey inner fence and the 98th percentile. Threshold values for over 59 elements, including emerging 'high-tech' critical elements such as lanthanides, Be, Ga or Ge, for which no EILs exist at present, are presented. <b>Citation:</b> Clemens Reimann, Patrice de Caritat, Establishing geochemical background variation and threshold values for 59 elements in Australian surface soil, <i>Science of The Total Environment</i>, Volume 578, 2017, Pages 633-648, ISSN 0048-9697, https://doi.org/10.1016/j.scitotenv.2016.11.010

Preamble -- The 'National Geochemical Survey of Australia: The Geochemical Atlas of Australia' was published in July 2011 along with a digital copy of the NGSA geochemical dataset (doi: 10.11636/Record.2011.020). The NGSA project is described here: www.ga.gov.au/ngsa. The present dataset contains additional geochemical data obtained on NGSA samples: the Plutonium Isotopes Dataset. Abstract -- Seventy three fine-fraction (<75 um) Top Outlet Sediment (TOS, 0 – 10 cm depth) NGSA samples from Queensland were analysed for the plutonium (Pu) isotopes 238Pu and 239+240Pu (unresolved 239Pu and 240Pu) to determine: (1) if Pu is detectable in the Australian environment; and (2) what the levels and ranges of Pu retention in selected Queensland catchment soils are. Radiochemical analyses were performed by alpha spectrometry at the radioanalytical laboratories of Radiation and Nuclear Sciences, Department of Health, Queensland, and at the Australian Radiation Protection and Nuclear Safety Agency (ARPANSA), Victoria. The method yielded a 239+240Pu trace-level detection limit of 0.04 mBq/g (equivalent to 10.4 fg/kg or 0.0056 net counts per minute) with a relative standard deviation (RSD) of 15.1%. The average tracer recovery was 69% (RSD 25%) over a 3-day count. Total analytical uncertainty ranged from 19% to 90% at close to detection limits. Field duplicate repeatability for 239+240Pu activity concentration ranged from 18% to 45%, which in part at least reflects the inherent heterogeneity of soil/sediments containing refractory particles exhibiting variation in Pu activity concentrations. Analytical duplicate repeatability for 239+240Pu activity concentration ranged from 10% to 23%, with the mean activity concentration and error of the replicates reported with propagation of errors. The results show a wide range of 239+240Pu activity concentration in the fine TOS NGSA samples across Queensland (N = 73): 239+240Pu: Min = <0.04 mBq/g; Med ± MAD (median absolute deviation) = 0.09 ± 0.07 mBq/g; Mean ± SD = 0.29 ± 0.72 mBq/g; 95th percentile = 1.53 mBq/g; Max = 4.88 mBq/g. In comparison the world average background is estimated at 0.2 mBq/g. Analytical results for 39% of samples were below detection. Six samples with 239+240Pu > 0.18 mBq/g (70th percentile) were also analysed for 238Pu by the same alpha spectrometry method. Results ranged from 0.04 to 0.1 mBq/g (N = 6). The complete dataset is available to download as a comma separated values (CSV) file from Geoscience Australia's website (https://pid.geoscience.gov.au/dataset/ga/144101).

The National Geochemical Survey of Australia (<a href="http://www.ga.gov.au/ngsa" title="NGSA website" target="_blank">NGSA</a>) is Australia’s only internally consistent, continental-scale <a href="http://dx.doi.org/10.11636/Record.2011.020" title="NGSA geochemical atlas and dataset" target="_blank">geochemical atlas and dataset</a>. The present dataset contains additional mineralogical data obtained on NGSA samples selected from the Darling-Curnamona-Delamerian (<a href="https://www.ga.gov.au/eftf/projects/darling-curnamona-delamerian" title="DCD website" target="_blank">DCD</a>) region of southeastern Australia for the first partial data release of the Heavy Mineral Map of Australia (HMMA) project. The HMMA, a collaborative project between Geoscience Australia and Curtin University underpinned by a pilot project establishing its feasibility, is part of the Australian Government-funded Exploring for the Future (<a href="https://www.ga.gov.au/eftf" title="EFTF website" target="_blank">EFTF</a>) program. The selected 223 NGSA sediment samples fall within the DCD polygon plus an approximately one-degree buffer. The samples were taken on average from 60 to 80 cm depth in floodplain landforms, dried and sieved to a 75-430 µm grainsize fraction, and the contained heavy minerals (HMs; i.e., those with a specific gravity >2.9 g/cm³) were separated by dense fluids and mounted on cylindrical epoxy mounts. After polishing and carbon-coating, the mounts were subjected to automated mineralogical analysis on a TESCAN® Integrated Mineral Analyzer (TIMA). Using scanning electron microscopy and backscatter electron imaging integrated with energy dispersive X-ray analysis, the TIMA identified over 140 different HMs in the DCD area. The dataset, consisting of over 29 million individual mineral grains identified, was quality controlled and validated by an expert team. The data released here can be visualised, explored and downloaded using an online, bespoke mineral network analysis tool (<a href="https://geoscienceaustralia.shinyapps.io/mna4hm/" title="MNA website" target="_blank">MNA</a>) built on a cloud-based platform. Accompanying this report are a data file of TIMA results and a mineralogy vocabulary file. When completed in 2023, it is hoped the HMMA project will positively impact mineral exploration and prospectivity modelling around Australia, as well as have other applications in earth and environmental sciences.

<div>With a higher demand for lithium (Li), a better understanding of its concentration and spatial distribution is important to delineate potential anomalous areas. This study uses a digital soil mapping framework to combine data from recent geochemical surveys and environmental covariates to predict and map Li content across the 7.6 million km2 area of Australia. Soil samples were collected by the National Geochemical Survey of Australia at a total of 1315 sites, with both top (0–10 cm depth) and bottom (on average 60–80 cm depth) catchment outlet sediments sampled. We developed 50 bootstrap models using a Cubist regression tree algorithm for both depths. The spatial prediction models were validated on an independent Northern Australia Geochemical Survey dataset, showing a good prediction with an RMSE of 3.82 mg kg-1 for the top depth. The model for the bottom depth has yet to be validated. The variables of importance for the models indicated that the first three Landsat bands and gamma radiometric dose have a strong impact on Li prediction. The bootstrapped models were then used to generate digital soil Li prediction maps for both depths, which could select and delineate areas with anomalously high Li concentrations in the regolith. The map shows high Li concentration around existing mines and other potentially anomalous Li areas. The same mapping principles can potentially be applied to other elements.&nbsp;</div> <b>Citation:</b> Ng, W., Minasny, B., McBratney, A., de Caritat, P., and Wilford, J.: Digital soil mapping of lithium in Australia, <i>Earth Syst. Sci. Data</i>, 15, 2465–2482, https://doi.org/10.5194/essd-15-2465-2023, <b>2023</b>.

Preamble: The 'National Geochemical Survey of Australia: The Geochemical Atlas of Australia' was published in July 2011 along with a digital copy of the NGSA geochemical dataset (http://dx.doi.org/10.11636/Record.2011.020). The NGSA project is described here: www.ga.gov.au/ngsa. The present dataset contains additional geochemical data obtained on NGSA samples: the Lead Isotopes Dataset. Abstract: Over 1200 new lead (Pb) isotope analyses were obtained on catchment outlet sediment samples from the NGSA regolith archive to document the range and patterns of Pb isotope ratios in the surface regolith and their relationships to geology and anthropogenic activity. The selected samples included 1204 NGSA Top Outlet Sediment (TOS) samples taken from 0 to 10 cm depth and sieved to <2 mm (or ‘coarse’ fraction); three of these were analysed in duplicate for a total of 1207 Pb isotope analyses. Further, 12 Northern Australia Geochemical Survey (NAGS; http://dx.doi.org/10.11636/Record.2019.002) TOS samples from within a single NGSA catchment, also sieved to <2 mm, were analysed to provide an indication of smaller scale variability. Combined, we thus present 1219 new TOS coarse, internally comparable data points, which underpin new national regolith Pb isoscapes. Additionally, 16 NGSA Bottom Outlet Sediment (BOS; ~60 to 80 cm depth) samples, also sieved to <2 mm, and 16 NGSA TOS samples sieved to a finer grainsize (<75 um, or ‘fine’) fraction from selected NGSA catchments were also included to inform on Pb mobility and residence. Lead isotope analyses were performed by Candan Desem as part of her PhD research at the School of Geography, Earth and Atmospheric Sciences, University of Melbourne. After an initial ammonium acetate (AmAc) leach, the samples were digested in aqua regia (AR). Although a small number of samples were analysed after the AmAc leach, all samples were analysed after the second, AR digestion, preparation step. The analyses were performed without prior matrix removal using a Nu Instruments Attom single collector Sector Field-Inductively Coupled Plasma-Mass Spectrometer (SF-ICP-MS). The dried soil digests were redissolved in 2% HNO3 run solutions containing high-purity thallium (1 ppb Tl) and diluted to provide ~1 ppb Pb in solution. Admixture of natural, Pb-free Tl (with a nominal 205Tl/203Tl of 2.3871) allowed for correction of instrumental mass bias effects. Concentrations of matrix elements in the diluted AR digests are estimated to be in the range of 1–2 ppm. The SF-ICP-MS was operated in wet plasma mode using a Glass Expansion cyclonic spray chamber and glass nebuliser with an uptake rate of 0.33 mL/min. The instrument was tuned for maximum sensitivity and provided ~1 million counts per second/ppb Pb while maintaining flat-topped peaks. Each analysis, performed in the Attom’s ‘deflector peak jump’ mode, consists of 30 sets of 2000 sweeps of masses 202Hg, 203Tl, 204Pb, 205Tl, 206Pb, 207Pb and 208Pb, with dwell times of 500 μs and a total analysis time of 4.5 min. Each sample acquisition was preceded by a blank determination. All corrections for baseline, sample Hg interference (202Hg/204Pb ratios were always <0.043) and mass bias were performed online, producing typical in-run precisions (2 standard errors) of ±0.047 for 206Pb/204Pb, ±0.038 for 207Pb/204Pb, ±0.095 for 208Pb/204Pb, ±0.0012 for 207Pb/206Pb and ±0.0026 for 208Pb/206Pb. A small number of samples with low Pb concentrations exhibited very low signal sizes during analysis resulting in correspondingly high analytical uncertainties. Samples producing within-run uncertainties of >1% relative (measured on the 207Pb/204Pb ratio) were discarded as being insufficiently precise to contribute meaningfully to the dataset. Data quality was monitored using interspersed analyses of Tl-doped ~1 ppb solutions of the National Institute of Standards and Technology (NIST) SRM981 Pb standard, and several silicate reference materials: United States Geological Survey ‘BCR-2’ and ‘AGV-2’, Centre de Recherches Pétrographiques et Géochimiques ‘BR’ and Japan Geological Survey ‘JB-2’. In a typical session, up to 50 unknowns plus 15 standards were analysed using an ESI SC-2 DX autosampler. Although previous studies using the Attom SF-ICP-MS used sample-standard-bracketing techniques to correct for instrumental Pb mass bias, Tl doping was found to produce precise, accurate and reproducible results. Based upon the data for the BCR-2 and AGV-2 secondary reference materials, for which we have the most analyses, deviations from accepted values (accuracy) were typically <0.17%. Data for the remaining silicate standards appear slightly less accurate but these results may, to some extent, reflect uncertainty in the assigned literature values for these materials. Replicate runs of selected AR digests yielded similar reproducibility estimates. The results show a wide range of Pb isotope ratios in the NGSA (and NAGS) TOS <2 mm fraction samples across the continent (N = 1219): 206Pb/204Pb: Min = 15.558; Med ± Robust SD = 18.844 ± 0.454; Mean ± SD = 19.047 ± 1.073; Max = 30.635 207Pb/204Pb; Min = 14.358; Med ± Robust SD = 15.687 ± 0.091; Mean ± SD = 15.720 ± 0.221; Max = 18.012 208Pb/204Pb; Min = 33.558; Med ± Robust SD = 38.989 ± 0.586; Mean ± SD = 39.116 ± 1.094; Max = 48.873 207Pb/206Pb; Min = 0.5880; Med ± Robust SD = 0.8318 ± 0.0155; Mean ± SD = 0.8270 ± 0.0314; Max = 0.9847 208Pb/206Pb; Min = 1.4149; Med ± Robust SD = 2.0665 ± 0.0263; Mean ± SD = 2.0568 ± 0.0675; Max = 2.3002 These data allow the construction of the first continental-scale regolith Pb isotope maps (206Pb/204Pb, 207Pb/204Pb, 208Pb/204Pb, 207Pb/206Pb, and 208Pb/206Pb isoscapes) of Australia and can be used to understand contributions of Pb from underlying bedrock (including Pb-rich mineralisation), wind-blown dust and possibly from anthropogenic sources (industrial, transport, agriculture, residential, waste handling). The complete dataset is available to download as a comma separated values (CSV) file from Geoscience Australia's website (http://dx.doi.org/10.26186/5ea8f6fd3de64). Isoscape grids (inverse distance weighting interpolated grids with a power coefficient of 2 prepared in QGis using GDAL gridding tool based on nearest neighbours) are also provided for the five Pb isotope ratios (IDW2NN.TIF files in zipped folder). Alternatively, the new Pb isotope data can be downloaded from and viewed on the GA Portal (https://portal.ga.gov.au/).

<div>Alluvial sediments have long been used in geochemical surveys as their compositions are assumed to be representative of areas upstream. Overbank and floodplain sediments, in particular, are increasingly used for regional to continental-scale geochemical mapping. However, during downstream transport, sediments from heterogeneous source regions are carried away from their source regions and mixed. Consequently, using alluvial sedimentary geochemical data to generate continuous geochemical maps remains challenging. In this study we demonstrate a technique that numerically unmixes alluvial sediments to make a geochemical map of their upstream catchments. The unmixing approach uses a model that predicts the concentration of elements in downstream sediments, given a map of the drainage network and element concentrations in the source region. To unmix sedimentary chemistry, we seek the upstream geochemical map that, when mixed downstream, best fits geochemical observations downstream. To prevent overfitting we penalise the roughness of the geochemical model. To demonstrate our approach we apply it to alluvial samples gathered as part of the Northern Australia Geochemical Survey. This survey gathered samples collected over a ∼ 500,000 km2 area in northern Australia. We first validate our approach for this sample distribution with synthetic tests, which indicate that we can resolve geochemical variability at scales greater than 0.5 – 1◦ in size. We proceed to invert real geochemical data from the total digestion of fine-grained fraction of alluvial sediments. The resulting geochemical maps for two elements of potential economic interest, Cu and Nd, are evaluated in detail. We find that in both cases, our predicted downstream concentrations match well against a held-out, unseen subset of the data, as well as against data from an independent geochemical survey. By performing principal component analysis on maps generated for all 46 available elements we produce a synthesis map showing the significant geochemical domains of this part of northern Australia. This map shows strong spatial similarities to the underlying lithological map of the area. Finally, we compare the results from our approach to a geochemical map produced by kriging. We find that, unlike the method presented here, kriging generates geochemical maps that are both dampened relative to expected magnitude, as well as being spatially distorted. We argue that the unmixing approach is the most appropriate method for generating geochemical maps from regional-scale alluvial surveys.&nbsp;</div> <b>Citation:</b> Alex G. Lipp, Patrice de Caritat, Gareth G. Roberts, Geochemical mapping by unmixing alluvial sediments: An example from northern Australia, <i>Journal of Geochemical Exploration,</i> Volume 248, <b>2023</b>, 107174, ISSN 0375-6742, https://doi.org/10.1016/j.gexplo.2023.107174. (https://www.sciencedirect.com/science/article/pii/S0375674223000213)