The association between content of the elements S, Cl, K, Fe, Cu, Zn and Br in normal and cirrhotic liver tissue from Danes and Greenlandic Inuit examined by dual hierarchical clustering analysis.

PROJECT: Meta-analysis of previous studies evaluating associations between content of elements sulphur (S), chlorine (Cl), potassium (K), iron (Fe), copper (Cu), zinc (Zn) and bromine (Br) in normal and cirrhotic autopsy liver tissue samples. PROCEDURE: Normal liver samples from 45 Greenlandic Inuit, median age 60 years and from 71 Danes, median age 61 years. Cirrhotic liver samples from 27 Danes, median age 71 years. Element content was measured using X-ray fluorescence spectrometry. STATISTICS: Dual hierarchical clustering analysis, creating a dual dendrogram, one clustering element contents according to calculated similarities, one clustering elements according to correlation coefficients between the element contents, both using Euclidian distance and Ward Procedure. RESULTS: One dendrogram separated subjects in 7 clusters showing no differences in ethnicity, gender or age. The analysis discriminated between elements in normal and cirrhotic livers. The other dendrogram clustered elements in four clusters: sulphur and chlorine; copper and bromine; potassium and zinc; iron. There were significant correlations between the elements in normal liver samples: S was associated with Cl, K, Br and Zn; Cl with S and Br; K with S, Br and Zn; Cu with Br. Zn with S and K. Br with S, Cl, K and Cu. Fe did not show significant associations with any other element. CONCLUSIONS: In contrast to simple statistical methods, which analyses content of elements separately one by one, dual hierarchical clustering analysis incorporates all elements at the same time and can be used to examine the linkage and interplay between multiple elements in tissue samples.

Nutrients and heavy metals distribution in thermally treated pig manure.

Ash from pig manure treated by combustion and thermal gasification was characterized and compared in terms of nutrient, i.e., potassium (K), phosphorus (P) and heavy metal, i.e., cadmium (Cd), chromium (Cr), copper (Cu), nickel (Ni) and zinc (Zn) contents. Total nutrient and metal concentrations were measured using energy dispersive X-ray fluorescence analysis. Acid (HNO3, H2SO4) and water-extractable concentrations were also measured both in non-classified ash and in selected ash particle size fractions using flame atomic absorption spectrometry and colorimetric spectrometry. Results indicate that ash from gasified manure contained more water-extractable K in comparison with combusted manure whereas the opposite was the case with respect to P. Heavy metals Ni, Cr and Cd were present in higher concentrations in the fine particle size fractions (< 30 microm of particle diameter), whereas K, P, Zn and Cu exhibited higher concentrations in the coarser particle size fractions (> 30 microm).

Multi-elemental EDXRF mapping of polluted soil from former horticultural land.

The distribution of major and trace elements was systematically investigated by use of energy dispersive X-ray fluorescence spectrometry (EDXRF) on a former horticultural soil. The purpose of the study was to combine mapping of soil element concentration levels with multivariate statistics for characterisation of soil metal pollution in relation to previous and present land use. A 1-ha study site was chosen from a former horticulture where a previous preliminary survey indicated increased concentration levels of toxic elements. The soil was sampled from the top 20 cm of the soil surface in a 10 x 10-m grid-like pattern covering the 1-ha study area. In addition, three soil profiles were studied. The elemental composition of the soil samples was investigated by EDXRF while the composition of aqueous soil extracts was determined by total reflection X-ray fluorescence spectrometry (TXRF). Based on mapping and multivariate statistically analysis of the data obtained by EDXRF, most elements were found in almost constant concentration levels in the top soil throughout the investigated site. However, the contents of the toxic elements Zn, Cu, As, and Pb were found to vary significantly within the area. Hence, the samples with high accumulations of As also contained relatively high amounts of Zn, Cu, and Pb, which indicates that toxic-element-containing pesticides have been applied to the soil surface in the area of the former green houses at the study site. The Pb/As mass ratio in the soil indicates that PbHAsO3 was the preferential lead arsenate used for pest management at the investigated site, while Cu as Bordeaux liquid (CuSO4) and Zn were applied to minimize the leaf damaging effect from the former compounds. Calculations indicated that As annually was applied to the soil in the former greenhouses in doses up to 4 kg As/ha while Pb had been annually applied in doses up to 12 kg Pb/ha. The enrichment of Zn, Cu, As and Pb was greatest in the top 20 cm of the soil and no anthropogenic enrichment of these elements occurred below a depth of 50 cm, indicating that the toxic elements are rather immobile in this soil. The results of this investigation suggest that EDXRF used in combination with multivariate statistics is a strong tool for multi-element mapping of elemental contents, sources and mobility in the terrestrial environment.