Estimation and usefulness of measurement uncertainty from sampling at different spatial scales: microns to kilometres.

Uncertainty of measurement values (MU) is crucial to their reliable geochemical interpretation. MU can be estimated using the Duplicate Method, which requires the taking of a small proportion of duplicated samples, and can be applied at any spatial scale. The distance between the duplicated samples is selected to reflect the effect of analyte heterogeneity on the measurement result (i.e. estimated concentration) within each sampling target, at the particular scale of investigation. Three published case studies, at different spatial scales, are used to explain how the Duplicate Method can be applied to estimate MU. They also illustrate how MU can be used to improve geochemical interpretation and validate measurement procedures (that include sampling) by judging their fitness for purpose. At the kilometre scale, measurements from the GEMAS survey of agricultural soils across Europe are used to estimate their MU for the first time. The MU for 53 elements range from an uncertainty factor of 1.01 to over 10. The MU contributes more that 20% to the total variance for 8 of the 53 elements, showing that the measurement procedure was not fit for purpose in those cases. At the micron scale, measurements of oxygen isotopes in candidate quartz reference materials had MU that was dominated by its sampling component, caused by sometimes unacceptable heterogeneity. A third case study of Pb in soils at 12 UK sites showed that the Duplicate Method can also be used to quantify the heterogeneity (as factor 1.03 to 2.4), and that it can indicate different possible sources of an element.

Factors controlling Mn and Zn contents in leaves of silver and downy birch in acidified soils of Central Europe and Norway.

In Central European mountain forests, foliar element concentrations (FECs) of manganese (Mn) in silver birch (Betula pendula Roth) are occasionally approximately 5000 mg kg-1 and can represent stress for these plants. Factors controlling the Mn FECs in silver birch in Central Europe and downy birch (Betula pubescens Ehrh.) in Norway have not yet been fully deciphered. In this study, the Central European silver birch specimens were sampled in 2022. The samples were analysed by X-ray fluorescence spectroscopy. Norwegian data were obtained from the literature. Mn FECs are commonly negatively correlated with magnesium and, in certain areas, with potassium. Mn FECs are simultaneously elevated with zinc (Zn), likely because of soil acidification and anthropogenic emissions. Mn FECs in birch were previously thought to be related to altitude, which was assigned to (i) downslope washes of Mn or (ii) the historical load of acid emissions. The highest Mn FECs in silver birch were found in the Harz Mountains, Germany, and have been attributed to historical atmospheric contamination and the abundance of soils on felsic silicic rocks poorly buffering acid rains. The historical emission load from iron and steel production was hypothesised to be the cause of elevated Mn and Zn FECs in the Beskid Mountains, Czech Republic. Mn FECs in birch can be used to map historical soil acidification caused by industrial emissions. Zn FECs in birches can reflect soil contamination by this element.

Wildfires as a Source of Potentially Toxic Elements (PTEs) in Soil: A Case Study from Campania Region (Italy).

The worldwide increase in fire events has attracted global attention, as potentially toxic elements (PTEs) have been widely recognised within the produced ash. Ash is transported, dispersed by wind, and deposited into the soil and surficial waters even far from fires. Considering that their composition can be enriched in PTEs, they represent a potential hazard for humans and other animals exposed to airborne particles and, afterwards, to resuspended matter, even at a considerable distance from the source. This study aimed to assess the environmental impact of fire events that occurred during the 2017 summer season at two different sites in the Campania region (Southern Italy). One of the fires affected a waste disposal site west of Caserta, and one involved a forest on the slopes of Mt. Somma-Vesuvius, a few kilometres southeast of Naples, the regional capital. Changes to the PTE concentration in the topsoil in the surroundings of both sites, after the fire events, were investigated. Enrichment factors (EFs) of a selection of PTEs were determined by comparing geochemical data from two sampling campaigns, one completed before and one after the fire events. A combined application of multivariate statistics (based on robust principal component analysis; RPCA) and geospatial analysis was used to determine the materials affected by the fire on the slopes of Mt. Somma-Vesuvius, and roughly locate their place. Specifically, a statistically significant enrichment of Hg was identified in the topsoil of both study areas. In addition, in soil samples collected at Mt. Somma-Vesuvius, more PTEs showed significant changes in their concentration. For both areas, Hg enrichments were related to the deposition of ash proceeding from waste burning; furthermore, as regards the soil of the Vesuvian area, Cr and Cd enrichments were associated with the fallout of ash generated during biomass combustion, and the increase in Cu and Zn concentrations was linked to the burning of crops on cultivated lands. Apart from the specific results obtained, concerning the examined case studies, the methods applied can be seen as a reliable option to determine the compositional characteristics of materials burned during a fire event, even with the prospect of improving the eventual assessment process of the related environmental hazards.

Forensic soil provenancing in an urban/suburban setting: A simultaneous multivariate approach.

Soil is a ubiquitous material at the Earth's surface with potential to be a useful evidence class in forensic and intelligence applications. Compositional data from a soil survey over North Canberra, Australian Capital Territory, are used to develop and test an empirical soil provenancing method. Mineralogical data from Fourier Transform InfraRed spectroscopy (FTIR) and geochemical data from X-Ray Fluorescence (XRF; for total major oxides) and Inductively Coupled Plasma-Mass Spectrometry (ICP-MS; for both total and aqua regia-soluble trace elements) are obtained from the survey's 268 topsoil samples (0-5 cm depth; 1 sample per km2 ). The simultaneous provenancing approach is underpinned by (i) the calculation of Spearman's correlation coefficients (rS ) between an evidentiary sample and all the samples in the database for all variables generated by each analytical method; and (ii) the preparation of an interpolated raster grid of rS for each evidentiary sample and method resulting in a series of provenance rasters ("heat maps"). The simultaneous provenancing method is tested on the North Canberra soil survey with three "blind" samples representing simulated evidentiary samples. Performance metrics of precision and accuracy indicate that the FTIR (mineralogy) and XRF (geochemistry) analytical methods offer the most precise and accurate provenance predictions. Maximizing the number of analytes/analytical techniques is advantageous in soil provenancing. Despite acknowledged limitations, it is concluded that the empirical soil provenancing approach can play an important role in forensic and intelligence applications.

Forensic soil provenancing in an urban/suburban setting: A sequential multivariate approach.

Compositional data from a soil survey over North Canberra, Australian Capital Territory, are used to develop and test an empirical soil provenancing method. Mineralogical data from Fourier transform infrared spectroscopy (FTIR) and magnetic susceptibility (MS), and geochemical data from X-ray fluorescence (XRF; for total major oxides) and inductively coupled plasma-mass spectrometry (ICP-MS; for both total and aqua regia-soluble trace elements) are performed on the survey's 268 topsoil samples (0-5 cm depth; 1 sample per km2 ). Principal components (PCs) are calculated after imputation of censored data and centered log-ratio transformation. The sequential provenancing approach is underpinned by (i) the preparation of interpolated raster grids of the soil properties (including PCs); (ii) the explicit quantification and propagation of uncertainty; (iii) the intersection of the soil property rasters with the values of the evidentiary sample (± uncertainty); and (iv) the computation of cumulative provenance rasters ("heat maps") for the various analytical techniques. The sequential provenancing method is tested on the North Canberra soil survey with three "blind" samples representing simulated evidentiary samples. Performance metrics of precision and accuracy indicate that the FTIR and MS (mineralogy), as well as XRF and total ICP-MS (geochemistry) analytical methods, offer the most precise and accurate provenance predictions. Inclusion of PCs in provenancing adds marginally to the performance. Maximizing the number of analytes/analytical techniques is advantageous in soil provenancing. Despite acknowledged limitations and gaps, it is concluded that the empirical soil provenancing approach can play an important role in forensic and intelligence applications.

Identification of spatial patterns, geochemical associations and assessment of origin-specific health risk of potentially toxic elements in soils of Armavir region, Armenia.

The study of soil potentially toxic elements (PTE) contents and establishment of the geochemical characterization of areas which have never been studied is of great concern. In 2019, soil survey of the Armavir region (Armenia) was conducted in order to investigate the spatial pattern of PTE, reveal PTE geochemical associations and assess the origin-specific health risks. The application of compositional data analysis and geospatial mapping allowed to identify two clusters of samples. The first cluster was spatially located on volcanic rocks and was represented by Fe, Co, Mn, Ti, Zn, Ba, Pb suggesting a natural origin of PTE in these areas. The second cluster was allocated on the alluvial, deluvial, and proluvial sediments and represented by As, Cu, Cr, Ni. Such combination of elements in the same group indicates the anthropogenic introduction of some quantities of PTE. The latter is confirmed by the presence of outliers and extreme values for As, Cu and Ni, as well as by the spatial colocation of Fe, Mn, Co, Pb, Zn outliers and extreme contents. The health risk assessment showed that for children the multi-elemental non-carcinogenic risk was detected, while for the adults the non-carcinogenic risk and carcinogenic risk were below the allowable level. The detailed study of the risk levels showed that in first cluster comparatively higher risk were observed for Pb, V, Ba, Zn while in the second cluster: Fe, Co, Mn, As, Cr, Cu, Ni. The results indicated the necessity of additional in-depth studies with special focus on bioavailability of PTE.

Aqueous inorganic uranium speciation in European stream waters from the FOREGS dataset using geochemical modelling and determination of a U bioavailability baseline.

The concentration of the bioavailable uranium fraction (Ubio) at the European scale was deduced by geochemical modelling considering several definitions found in the literature and the FOREGS European stream waters geochemical atlas dataset to produce a Ubio baseline. A sensitivity analysis was performed using three thermodynamic databases. We also investigated the link between total dissolved uranium (Uaq) concentrations, speciation and global stream water chemistry on the one hand, and the lithology and ages of the surrounding rocks on the other. The more U-enriched the stream sediments or rock type contexts are, which tends to be the case with rocks containing silicates (4.1 mg/kg), the less U-concentrated the stream waters are (0.15 µg/L). Sedimentary rocks lead to slightly higher Uaq concentrations (0.34 µg/L) even if the concentration in sediment (Used) is relatively low (1.6 mg/kg). This trend is reversed for Ubio, with higher concentrations in a crystalline context. The mean estimated Ubio value ranges from 1.5.10-3 to 65.3 ng/L and can fluctuate by 3 orders of magnitude depending on the considered definition as opposed to by 2 orders of magnitude accountable to differences between thermodynamic databases. The classification of the water in relation to the two surrounding rock lithologies makes it possible to reduce the mean variability for the Ubio concentrations. Irrespective of the definition of Ubio considered, in 59% of cases the Ubio fraction represents less than 1% of Uaq. Several threshold values relating to Ubio were proposed, assuming knowledge only of the aqueous concentrations of the major elements and Uaq.

Discrimination of topsoil environments in a karst landscape: an outcome of a geochemical mapping campaign.

The study presented in this work emerged as a result of a multiyear regional geochemical survey based on low-density topsoil sampling and the ensuing geochemical atlas of Croatia. This study focuses on the Dinaric part of Croatia to expound the underlying mechanisms controlling the mobilities and variations in distribution of potentially harmful elements as observed from different environmental angles. Although serious environmental degradation of the vulnerable karst soil landscapes was expected to occur chiefly through the accumulation of various heavy metals, the most acute threat materialized through the soil acidification (Al-toxicity) affecting the entire Dinaric karst area. This picture surfaced from the analysis of all three investigated discriminant function models employing the abovementioned environmental criteria selected autonomously with respect to the evaluated soil geochemistry, namely, geologic setting, regional placement and land use. These models are presented by not only the characteristic discriminant-function diagrams but also a set of appropriate mathematically derived geochemical maps disclosing the allocations of potential threats to the karst soil landscapes posed by soil acidity.

Source and background threshold values of potentially toxic elements in soils by multivariate statistics and GIS-based mapping: a high density sampling survey in the Parauapebas basin, Brazilian Amazon.

A high-density regional-scale soil geochemical survey comprising 727 samples (one sample per each 5 × 5 km grid) was carried out in the Parauapebas sub-basin of the Brazilian Amazonia, under the Itacaiúnas Basin Geochemical Mapping and Background Project. Samples were taken from two depths at each site: surface soil, 0-20 cm and deep soil, 30-50 cm. The ground and sieved (< 75 µm) fraction was digested using aqua regia and analyzed for 51 elements by inductively coupled plasma mass spectrometry (ICPMS). All data were used here, but the principal focus was on the potential toxic elements (PTEs) and Fe and Mn to evaluate the spatial distribution patterns and to establish their geochemical background concentrations in soils. Geochemical maps as well as principal component analysis (PCA) show that the distribution patterns of the elements are very similar between surface and deep soils. The PCA, applied on clr-transformed data, identified four major associations: Fe-Ti-V-Sc-Cu-Cr-Ni (Gp-1); Zr-Hf-U-Nb-Th-Al-P-Mo-Ga (Gp-2); K-Na-Ca-Mg-Ba-Rb-Sr (Gp-3); and La-Ce-Co-Mn-Y-Zn-Cd (Gp-4). Moreover, the distribution patterns of elements varied significantly among the three major geological domains. The whole data indicate a strong imprint of local geological setting in the geochemical associations and point to a dominant geogenic origin for the analyzed elements. Copper and Fe in Gp-1 were enriched in the Carajás basin and are associated with metavolcanic rocks and banded-iron formations, respectively. However, the spatial distribution of Cu is also highly influenced by two hydrothermal mineralized copper belts. Ni-Cr in Gp-1 are highly correlated and spatially associated with mafic and ultramafic units. The Gp-2 is partially composed of high field strength elements (Zr, Hf, Nb, U, Th) that could be linked to occurrences of A-type Neoarchean granites. The Gp-3 elements are mobile elements which are commonly found in feldspars and other rock-forming minerals being liberated by chemical weathering. The background threshold values (BTV) were estimated separately for surface and deep soils using different methods. The '75th percentile', which commonly used for the estimation of the quality reference values (QRVs) following the Brazilian regulation, gave more restrictive or conservative (low) BTVs, while the 'MMAD' was more realistic to define high BTVs that can better represent the so-called mineralized/normal background. Compared with CONAMA Resolution (No. 420/2009), the conservative BTVs of most of the toxic elements were below the prevention limits (PV), except Cu, but when the high BTVs are considered, Cu, Co, Cr and Ni exceeded the PV limits. The degree of contamination (Cdeg), based on the conservative BTVs, indicates low contamination, except in the Carajás basin, which shows many anomalies and had high contamination mainly from Cu, Cr and Ni, but this is similar between surface and deep soils indicating that the observed high anomalies are strictly related to geogenic control. This is supported when the Cdeg is calculated using the high BTVs, which indicates low contamination. This suggests that the use of only conservative BTVs for the entire region might overestimate the significance of anthropogenic contamination; thus, we suggest the use of high BTVs for effective assessment of soil contamination in this region. The methodology and results of this study may help developing strategies for geochemical mapping in other Carajás soils or in other Amazonian soils with similar characteristics.

Assessment of organic and metallic contamination in the surface sediment of Monastir Bay (Eastern Tunisia): Spatial distribution, potential sources, and ecological risk assessment.

To investigate the current environment status in Monastir Bay (Tunisia), surface sediments from 32 stations were assessed for heavy metal and organic matter concentrations, and the results were compared with values of natural metal content, marine sediment quality standards, and other results concerning sediments from other Mediterranean coasts. The study of their spatial distributions refined by complementary approaches, including potential ecological risks determined through the enrichment factor, geo-accumulation index, contamination factor, potential ecological risk index, pollution load index, and principal component analysis, showed a significant impact of multiple anthropogenic sources. Moderate pollution of sediments, particularly by Ni and Cu, was also observed. Moreover, TOC values showed that the northern part of Monastir Bay is characterized by high levels of sediment organic matter because of the presence of fish farm cage. This baseline study can be used to establish background values for future sediment surveys.

Geochemical characteristics of soil of the city of Skopje, Republic of Macedonia.

This study represents the first systematic investigation of the spatial distribution of different chemical elements in the soil of the city of Skopje, Republic of Macedonia. For this purpose, surface soil samples from 234 locations were analyzed to determine the content of 20 major and trace elements (Ag, Al, As, Ba, Ca, Cd, Cr, Cu, Fe, K, Li, Mg, Mn, Na, Ni, P, Pb, Sr, V and Zn) to assess the size of the areas eventually affected by heavy metal pollution. All samples were analyzed by atomic emission spectroscopy with inductively coupled plasma (ICP-AES). Cluster and factor analysis (R-mode) were applied in order to show the associations of chemical elements. Four factors were obtained: Factor 1 (K, Na, Ba and Al), Factor 2 (Cr, Ni, Mg and Fe), Factor 3 (Zn, Cd and Cu) and Factor 4 (Sr and Ca). It was established that the distribution of the associations of F1, F2 and F4 are mostly as a result of the complex geology and lithology of the region while the association of F3 represents an anthropogenic association.

Human impacts recorded in chemical and isotopic fingerprints of soils from Dunedin City, New Zealand.

We present results from the first urban chemical and isotopic soil baseline survey to be completed for a New Zealand city. The major, minor, trace and isotopic composition of soils from different depths across the city of Dunedin are shown to be spatially variable due to geogenic and anthropogenic influences. Based on Principal component analysis (PCA) for the shallow soil depth, at least 40% (PC1 and PC3) of the dataset variance is attributed to a geogenic source. Soils enriched in Al, Cr, Fe, Hf, Mo, Ni, Th, Ti, U, V and Zr (PC1) are spatially associated with mapped units of the basaltic Dunedin Volcanic Group, indicating a geogenic source. An anthropogenic influence is attributed to at least 23% (PC2 and PC5) of the dataset variance. The chemical elements As, B, Bi, Cd, Cu, P, Pb, Sb, Sn and Zn (PC2) are strongly spatially associated with soils sampled above high-density urban residential, commercial and industrial sites, and are interpreted to reflect heavy metal contamination from human activities. In conjunction with historical vehicle emissions from leaded petrol, we suggest that legacy leaded paint from residential, commercial and industrial buildings flaking into Dunedin City soils is a significant contributor to Pb in the Dunedin urban environment. Median heavy metal contents for shallow soils (0-2 cm) from a variety of land-uses throughout Dunedin City are shown to be almost an order of magnitude greater than median heavy metal concentrations in soils from regional baselines. Significantly, urban anthropogenic sources of heavy metals, and C, N and S isotopes are shown to exert a stronger influence on soil composition than rural anthropogenic sources. Results from this study provide an important case-study for urban soil contamination for a relatively young city from the Southern Hemisphere, for which there are currently few examples.

Spatial relationship between the field-measured ambient gamma dose equivalent rate and geological conditions in a granitic area, Velence Hills, Hungary: An application of digital spatial analysis methods.

In order to estimate the annual dose that the public receive from natural radioactivity, the identification of the potential risk areas is required which, in turn, necessitates understanding the relationship between the spatial distribution of natural radioactivity and the geogenic risk factors (e.g., rock types, presence of dikes, faults, physical conditions of soil, etc.). A detailed spatial analysis of outdoor ambient gamma dose equivalent rate was performed in the western side of Velence Hills, the largest outcropped granitic area in Hungary. In order to assess the role of local geology in the spatial distribution of gamma dose rates, field measurements were carried out at ground level at 300 sites along a 250 m x 250 m regular grid in a total surface of 19.8 km2. Digital image processing methods were applied to identify anomalies, heterogeneities and spatial patterns in the measured gamma dose rates, including local maxima and minima determination, digital cross sections, gradient magnitude and gradient direction, second derivative profile curvature, local variability, lineament density, 2D autocorrelation and directional variogram analyses. Statistical inference shows that different gamma dose rate levels are associated with the geological formations, with the highest level on the Carboniferous granite including outlying values. Moreover, digital image processing reveales that linear gamma dose rate spatial features are parallel to the SW-NE dike system and to the NW-SE main fractures. The results of this study underline the importance of understanding the role of geogenic risk factors influencing the ambient gamma dose equivalent rate received by public. The study also demonstrates the power of the image processing techniques for the identification of spatial pattern in field-measured geogenic radiation.

Regional geochemical baseline concentration of potentially toxic trace metals in the mineralized Lom Basin, East Cameroon: a tool for contamination assessment.

The distribution of trace metals in active stream sediments from the mineralized Lom Basin has been evaluated. Fifty-five bottom sediments were collected and the mineralogical composition of six pulverized samples determined by XRD. The fine fraction (< 150 µm) was subjected to total digestion (HClO4 + HF + HCl) and analyzed for trace metals using a combination of ICP-MS and AAS analytical methods. Results show that the mineralogy of stream sediments is dominated by quartz (39-86%), phyllosilicates (0-45%) and feldspars (0-27%). Mean concentrations of the analyzed metals are low (e.g. As = 99.40 µg/kg, Zn = 573.24 µg/kg, V = 963.14 µg/kg and Cr = 763.93 µg/kg). Iron and Mn have significant average concentrations of 28.325 and 442 mg/kg, respectively. Background and threshold values of the trace metals were computed statistically to determine geochemical anomalies of geologic or anthropogenic origin, particularly mining activity. Factor analysis, applied on normalized data, identified three associations: Ni-Cr-V-Co-As-Se-pH, Cu-Zn-Hg-Pb-Cd-Sc and Fe-Mn. The first association is controlled by source geology and the neutral pH, the second by sulphide mineralization and the last by chemical weathering of ferromagnesian minerals. Spatial analysis reveals similar distribution trends for Co-Cr-V-Ni and Cu-Zn-Pb-Sc reflecting the lithology and sulphide mineralization in the basin. Relatively high levels of As were concordant with reported gold occurrences in the area while Fe and Mn distribution are consistent with their source from the Fe-bearing metamorphic rocks. These findings provide baseline geochemical values for common and parallel geological domains in the eastern region of Cameroon. Although this study shows that the stream sediments are not polluted, the evaluation of metal composition in environmental samples from abandoned and active mine sites for comparison and environmental health risk assessment is highly recommended.

Assessment of potentially harmful elements pollution in the Calore River basin (Southern Italy).

The geographical distribution of concentration values for harmful elements was determined in the Campania region, Italy. The study area consists of the drainage basin of the River Calore, a tributary of the river Volturno, the largest Southern Italian river. The results provide reliable analytical data allowing a quantitative assessment of the trace element pollution threat to the ecosystem and human health. Altogether 562 stream sediment samples were collected at a sampling density of 1 site per 5 km2. All samples were air-dried, sieved to <100 mesh fraction and analyzed for 37 elements after an aqua regia extraction by a combination of ICP-AES and ICP-MS. In addition to elemental analysis, gamma-ray spectrometry data were collected (a total of 562 measurements) using a hand-held Scintrex GRS-500 spectrometer. Statistical analyses were performed to show the single-element distribution and the distribution of elemental association factor scores resulting from R-mode factor analyses. Maps showing element distributions were made using GeoDAS and ArcGIS software. Our study showed that, despite evidence from concentrations of many elements for enrichment over natural background values, the spatial distribution of major and trace elements in Calore River basin is determined mostly by geogenic factors. The southwestern area of the basin highlighted an enrichment of many elements potentially harmful for human health and other living organisms (Al, Fe, K, Na, As, Cd, La, Pb, Th, Tl, U); however, these anomalies are due to the presence of pyroclastic and alkaline volcanic lithologies. Even where sedimentary lithologies occur, many harmful elements (Co, Cr, Mn, Ni) showed high concentration levels due to natural origins. Conversely, a strong heavy metal contamination (Pb, Zn, Cu, Sb, Ag, Au, Hg), due to an anthropogenic contribution, is highlighted in many areas characterized by the presence of road junctions, urban settlements and industrial areas. The enrichment factor of these elements is 3-4 times higher than the background values. The southwestern area of the basin is characterized by a moderate/high degree of contamination, just where the two busiest roads of the area run and the highest concentration of industries occurs.

Multivariate spatial analyses of the distribution and origin of trace and major elements in soils surrounding a secondary lead smelter.

Major and trace elements in soils originate from natural processes and different anthropogenic activities which are difficult to discriminate. On a 17-ha impacted site in northern France, two industrial sources of soil contamination were xidentified: a former iron foundry and a current secondary lead smelter. To discriminate and map natural and anthropogenic sources of major and trace elements on this site, the rarely applied MULTISPATI-principal component analysis (PCA) method was used. Using a 20-m × 20-m grid, 247 topsoil horizons were sampled and analysed with a field-portable X-ray fluorescence analyser for screening soil contamination. The study site was heavily contaminated with Pb and, to a lesser degree, with Sn. Summary statistics and enrichment factors allowed the differentiation of the main lithogenic or anthropogenic origin of the elements. The MULTISPATI-PCA method, which explained 73.9 % of the variability with the three first factors, evidenced strong spatial structures. Those spatial structures were attributed to different natural and artificial processes in the study area. The first axis can be interpreted as a lithogenic effect. Axes 2 and 3 reflect the two different contamination sources. Pb, Sn and S originated from the secondary lead smelter while Fe and Ca were mainly derived from the old iron foundry activity and the old railway built with foundry sand. This study demonstrated that the MULTISPATI-PCA method can be successfully used to investigate multicontaminated sites to discriminate the various sources of contamination.

Natural and man-made radionuclides in sediments of an inlet in Rio de Janeiro State, Brazil.

The distribution of natural radionuclides (226)Ra, (228)Ra, (40)K and man-made radionuclides ((54)Mn, (60)Co and (137) Cs) in the surface sediments of an inlet of Ribeira Bay were investigated. Sediment samples were collected and analyzed for radionuclides, organic matter, carbonate, sulfate, cationic exchange capacity and grain size composition. The natural radionuclide concentrations ranged from 4.4 to 45, from 10 to 93, from 66 to 1347Bq·kg(-1) dry weight for (226)Ra, (228)Ra and (40)K, respectively. Natural radionuclide concentrations tend to be higher in the silt fraction, which determines their pattern distributions. Only one sample presented measurable concentration for (137)Cs, while (54)Mn was detected in two samples and (60)Co in four sediment samples. Man-made radionuclides present a maximum value of dose external four times lower than the normal background and the potential risk due to the presence of man-made radionuclides in sediments is lower than the risk provided by the natural radionuclides.

Multi-element geochemical mapping in Southern China.

The 76-element Geochemical Mapping (76 GEM) Project was undertaken in southwestern China in 2000 and in southeastern China in 2008. In this project, 5244 composite samples of stream sediment at a density of one composite sample for each 1:50,000-scale map sheet were prepared from sample archives of the China Regional Geochemistry-National Reconnaissance (RGNR) Project, which have been available since 1978. The 76 elements were analyzed by using inductively coupled plasma mass spectrometry (ICP-MS), X-ray fluorescence (XRF), and inductively coupled plasma atomic emission spectroscopy (ICP-AES). In the present study, a new quality-control method known as the visualized standard map method was applied to the results of the 76 GEM project. Mean value and background value, which indicate the average concentration of the 76 elements in southern China, were derived from statistical data. Moreover, geochemical maps were compiled to demonstrate the distribution of the 76 elements in southern China.