The single component geochemical map: Fact or fiction?

Single component geochemical maps are the most basic representation of spatial elemental distributions and commonly used in environmental and exploration geochemistry. However, the compositional nature of geochemical data imposes several limitations on how the data should be presented. The problems relate to the constant sum problem (closure), and the inherently multivariate relative information conveyed by compositional data. Well known is, for instance, the tendency of all heavy metals to show lower values in soils with significant contributions of diluting elements (e.g., the quartz dilution effect); or the contrary effect, apparent enrichment in many elements due to removal of potassium during weathering. The validity of classical single component maps is thus investigated, and reasonable alternatives that honour the compositional character of geochemical concentrations are presented. The first recommended such method relies on knowledge-driven log-ratios, chosen to highlight certain geochemical relations or to filter known artefacts (e.g. dilution with SiO2 or volatiles). This is similar to the classical normalisation approach to a single element. The second approach uses the (so called) log-contrasts, that employ suitable statistical methods (such as classification techniques, regression analysis, principal component analysis, clustering of variables, etc.) to extract potentially interesting geochemical summaries. The caution from this work is that if a compositional approach is not used, it becomes difficult to guarantee that any identified pattern, trend or anomaly is not an artefact of the constant sum constraint. In summary the authors recommend a chain of enquiry that involves searching for the appropriate statistical method that can answer the required geological or geochemical question whilst maintaining the integrity of the compositional nature of the data. The required log-ratio transformations should be applied followed by the chosen statistical method. Interpreting the results may require a closer working relationship between statisticians, data analysts and geochemists.

Multivariate analysis of regional-scale geochemical data for environmental monitoring

A compositional multivariate approach is used to analyse regional scale soil geochemical data obtained as part of the Tellus Project generated by the Geological Survey Northern Ireland (GSNI). The multi-element total concentration data presented comprise XRF analyses of 6862 rural soil samples collected at 20cm depths on a non-aligned grid at one site per 2 km2. Censored data were imputed using published detection limits. Using these imputed values for 46 elements (including LOI), each soil sample site was assigned to the regional geology map provided by GSNI initially using the dominant lithology for the map polygon. Northern Ireland includes a diversity of geology representing a stratigraphic record from the Mesoproterozoic, up to and including the Palaeogene. However, the advance of ice sheets and their meltwaters over the last 100,000 years has left at least 80% of the bedrock covered by superficial deposits, including glacial till and post-glacial alluvium and peat. The question is to what extent the soil geochemistry reflects the underlying geology or superficial deposits. To address this, the geochemical data were transformed using centered log ratios (clr) to observe the requirements of compositional data analysis and avoid closure issues. Following this, compositional multivariate techniques including compositional Principal Component Analysis (PCA) and minimum/maximum autocorrelation factor (MAF) analysis method were used to determine the influence of underlying geology on the soil geochemistry signature. PCA showed that 72% of the variation was determined by the first four principal components (PC’s) implying “significant” structure in the data. Analysis of variance showed that only 10 PC’s were necessary to classify the soil geochemical data. To consider an improvement over PCA that uses the spatial relationships of the data, a classification based on MAF analysis was undertaken using the first 6 dominant factors. Understanding the relationship between soil geochemistry and superficial deposits is important for environmental monitoring of fragile ecosystems such as peat. To explore whether peat cover could be predicted from the classification, the lithology designation was adapted to include the presence of peat, based on GSNI superficial deposit polygons and linear discriminant analysis (LDA) undertaken. Prediction accuracy for LDA classification improved from 60.98% based on PCA using 10 principal components to 64.73% using MAF based on the 6 most dominant factors. The misclassification of peat may reflect degradation of peat covered areas since the creation of superficial deposit classification. Further work will examine the influence of underlying lithologies on elemental concentrations in peat composition and the effect of this in classification analysis.