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X-ray fluorescence (XRF) spectroscopy offers a fast and efficient method for analysing soil elemental composition, both in the laboratory and the field. However, the technique is sensitive to spectral interference as well as physical and chemical matrix effects, which can reduce the precision of the measurements. We systematically assessed the XRF technique under different sample preparations, water contents, and excitation times. Four different soil samples were used as blocks in a three-way factorial experiment, with three sample preparations (natural aggregates, ground to ≤2 mm and ≤1 mm), three gravimetric water contents (air-dry, 10% and 20%), and three excitation times (15, 30 and 60 s). The XRF spectra were recorded and gave 540 spectra in all. Elemental peaks for Si, K, Ca, Ti, Fe and Cu were identified for analysis. We used analysis of variance (anova) with post hoc tests to identify significant differences between our factors and used the intensity and area of the elemental peaks as the response. Our results indicate that all of these factors significantly affect the XRF spectrum, but longer excitation times appear to be more defined. In most cases, no significant difference was found between air-dry and 10% water content. Moisture has no apparent effect on coarse samples unless ground to 1 mm. We suggested that the XRF measurements that take 60 s from dry samples or only slightly moist ones might be an optimum option under field conditions.

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Soil salinization resulting from shallow saline groundwater is a major global environmental issue causing land degradation, especially in semi-arid regions such as Australia. The adverse impact of shallow saline groundwater on soil salinization varies in space and time due to the variation in groundwater levels and salt concentration. Understanding the spatio-temporal variation is therefore vital to develop an effective salinity management strategy. In New South Wales, Australia, a hydrogeological landscape unit approach is generally applied, based on spatial information and expert operators, classifying the landscape in relation to landscape and climate. In this paper, a data science approach (random forest model) is introduced, based on historical groundwater quality and quantity data providing predictions in a 4-dimensional space. As a case study, we demonstrate the spatio-temporal factors impacting standing water levels (SWL) and associated salinity and predict the spatial and temporal variability in the Muttama catchment (1059 km2), in NSW, south eastern Australia. The random forest model explains 77% of the variance in the groundwater salinity (electrical conductivity) and 65% of the SWL. Spatial factors were the most significant variables determining the space-time variation in groundwater salinity and the occurrence of groundwater at the surface. Drilled piezometer depth and elevation are dominant factors controlling SWL, while salinity is mainly determined by underlying geology. The methodology in this study predicts salinity and SWL in the landscape at fine scales, through time, improving options for salinity management.

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While traditional laboratory methods of determining soil organic carbon (SOC) content are generally simple, this becomes more challenging when carbonates are present in the soil; such is commonly found in semi-arid areas. Additionally, soil inorganic carbon (SIC) content itself is difficult to determine. This study uses visible near infrared (VisNIR) spectra to predict SOC and SIC contents of samples, and the impact of including soil pH and soil total carbon (STC) data as predictor variables was evaluated. The results indicated that combining available soil pH and STC content data with VisNIR spectra dramatically improved prediction accuracy of the Cubist models. Using the full suite of predictor variables, Cubist models trained on the calibration dataset (75%) could predict the validation dataset (25%) for SOC content with a Lin's concordance correlation coefficient (LCCC) of 0.94, and an LCCC of 0.83 for SIC content. This is compared to an LCCC of 0.81 and 0.35 for SOC and SIC content, respectively, when no ancillary soil data was included with VisNIR spectra as predictor variables. These results suggest that there may be promise for using other readily available soil data in combination with VisNIR spectra to improve the predictions of different soil properties. •It can be laborious and expensive to measure soil organic and inorganic carbon content with traditional laboratory methods, and there has been recent focus on using spectroscopic techniques to overcome this.•This study demonstrates that combining ancillary soil data (pH and total carbon content) with these spectroscopic techniques can considerably improve predictions of SOC and SIC content.

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This study investigated the spatial variability of total and phosphate-extractable arsenic (As) concentrations in soil adjacent to a cattle-dip site, employing a linear mixed model-based geostatistical approach. The soil samples in the study area (n = 102 in 8.1 m(2)) were taken at the nodes of a 0.30 × 0.35 m grid. The results showed that total As concentration (0-0.2 m depth) and phosphate-extractable As concentration (at depths of 0-0.2, 0.2-0.4, and 0.4-0.6 m) in soil adjacent to the dip varied greatly. Both total and phosphate-extractable soil As concentrations significantly (p = 0.004-0.048) increased toward the cattle-dip. Using the linear mixed model, we suggest that 5 samples are sufficient to assess a dip site for soil (As) contamination (95% confidence interval of ±475.9 mg kg(-1)), but 15 samples (95% confidence interval of ±212.3 mg kg(-1)) is desirable baseline when the ultimate goal is to evaluate the effects of phytoremediation. Such guidelines on sampling requirements are crucial for the assessment of As contamination levels at other cattle-dip sites, and to determine the effect of phytoremediation on soil As.

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