Elsevier

Applied Geochemistry

Volume 14, Issue 4, June 1999, Pages 423-432
Applied Geochemistry

Geochemistry of natural and anthropogenic fall-out (aerosol and precipitation) collected from the NW Mediterranean: two different multivariate statistical approaches

https://doi.org/10.1016/S0883-2927(98)00062-6Get rights and content

Abstract

The chemical characteristics of the mineral fractions of aerosol and precipitation collected in Sardinia (NW Mediterranean) are highlighted by means of two multivariate statistical approaches. Two different combinations of classification and statistical methods for geochemical data are presented. It is shown that the application of cluster analysis subsequent to Q-Factor analysis better distinguishes among Saharan dust, background pollution (Europe-Mediterranean) and local aerosol from various source regions (Sardinia). Conversely, the application of simple cluster analysis was able to distinguish only between aerosols and precipitation particles, without assigning the sources (local or distant) to the aerosol. This method also highlighted the fact that crust-enriched precipitation is similar to desert-derived aerosol. Major elements (Al, Na) and trace metal (Pb) turn out to be the most discriminating elements of the analysed data set. Independent use of mineralogical, granulometric and meteorological data confirmed the results derived from the statistical methods employed.

Introduction

Statistical analysis in atmospheric studies is a well-known and well-developed field (Morandi et al., 1987; Hopke, 1988; Van Malderen et al., 1992). This study presents an example of the use of cluster analysis (CA), Q-Factor analysis (Q-FA) and discriminant analysis (DA) in atmospheric geochemistry, in an attempt to classify mixed aerosol and precipitation samples on the basis of their major element and trace metal chemistry.

Atmospheric inputs to the Mediterranean are of particular interest, in view of the different areas of aerosol production on the north and south belts.

The principal source of natural “crustal” material in the Mediterranean is the Sahara, while industrialised and semi-industrialised Northern Europe is a source of anthropogenic “background” material to the atmosphere. These inputs have an important influence on both the mineralogical and chemical composition of the Mediterranean aerosol. Previous works have shown that the bulk aerosol in the lower troposphere in this area has two main components: sea salt aerosol and mineral aerosol (Bergametti et al., 1989; Correggiari et al., 1989; Chester et al., 1993a).

These aerosols are removed from the atmosphere to the sea surface by a combination of “dry” (i.e., not involving aqueous phase) and “wet” (precipitation scavenging) depositional modes, and these modes are geochemically different with respect to the solutions with which the aerosols come into contact. Estimates of dust transport and deposition in the Mediterranean have been made by the Group of Experts on the Scientific Aspects of Marine Pollution (GESAMP, 1989) using a model. The temporal variability of dust deposition rates may vary greatly because of the strong seasonal cycle in dust concentrations and the large seasonal variability of precipitation rates (Prospero, 1996).

The present study is based on a collection of 6-month aerosol samples and one-year precipitation samples at a remote site. An overall sampling program was applied to investigate the geochemistry of natural (Saharan dust) and anthropogenic (background) aerosols and to separate local versus distant inputs to the Western Mediterranean (Guerzoni et al., 1997). If and how crust-enriched precipitation is similar to desert-derived aerosol was also verified.

Two different ways of treating the data sets were planned, as follows:

  • 1.

    a rank transformation was applied to the data and subsequently CA on the ranked data, followed by DA on the CA groups;

  • 2.

    the data matrix was first reduced on the basis of Q-FA on the ranked data; then CA was applied to samples, with factor loading as new variables, and then DA on the CA groups.

The aims of this paper were to present the geochemical composition of insoluble aerosol and suspended particulate in precipitation and to show two different multivariate statistical approaches to the data sets; and then to translate statistical results into meaningful geological statements. The contributions of local versus distant sources were particularly highlighted.

Section snippets

Sampling

Chemical data of the insoluble fraction of aerosols collected at a land-based coastal station in SE Sardinia, Western Mediterranean (9° long E, 39° lat N) (Fig. 1) are presented, together with measurements on mineral particulate deposited with precipitation. A total of 86 samples (55 aerosol; 31 rain) were collected during the period October 1990/October 1991, and 69 of these (55 aerosol; 14 rain) are presented here. The remaining 17 rain samples were not analysed due to the low concentration

Measurements in air and rain

Table 1 lists arithmetic and geometric means for insoluble fractions in aerosol and rain. The overall means are 6 μg m−3 and 26 mg l−1, with significant differences between samples collected from winds from the south, called Saharan, and samples from all other directions, called Background. This classification was also carried out prior to chemical analysis, using a suite of meteorological data, together with back-trajectories. Table 2 shows the wind component of particle concentrations in

Conclusions

Concurrent sampling of aerosol and precipitation is useful in comparing contents of the insoluble fraction of air particulate.

The statistical methods used in this study are well known, and commonly used in situations in which the interplay of many sources of variation do not allow an objective and comprehensive method of describing physical phenomena. Divergent results are obtained by applying two different combinations of classification and statistical methods to geochemical data.

In the first

Acknowledgements

This paper is IGM-CNR No. 1083. We thank F. Visin and G. Quarantotto for chemistry work, and G. Walton for revision of the English text. We also thank Prof. P. Mantovan and Dr A. Pastore for assistance in the review of the statistical procedures.

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