Characterisation of the dilute HCl extraction method for the identification of metal contamination in Antarctic marine sediments

A regional survey of potential contaminants in marine or estuarine sediments is often one of the first steps in a post-disturbance environmental impact assessment. Of the many different chemical extraction or digestion procedures that have been proposed to quantify metal contamination, partial acid extractions are probably the best overall compromise between selectivity, sensitivity, precision, cost and expediency. The extent to which measured metal concentrations relate to the anthropogenic fraction that is bioavailable is contentious, but is one of the desired outcomes of an assessment or prediction of biological impact. As part of a regional survey of metal contamination associated with Australia's past waste management activities in Antarctica, we wanted to identify an acid type and extraction protocol that would allow a reasonable definition of the anthropogenic bioavailable fraction for a large number of samples. From a kinetic study of the 1 M HCl extraction of two Certified Reference Materials (MESS-2 and PACS-2) and two Antarctic marine sediments, we concluded that a 4 h extraction time allows the equilibrium dissolution of relatively labile metal contaminants, but does not favour the extraction of natural geogenic metals. In a regional survey of 88 marine samples from the Casey Station area of East Antarctica, the 4 h extraction procedure correlated best with biological data, and most clearly identified those sediments thought to be contaminated by runoff from abandoned waste disposal sites. Most importantly the 4 h extraction provided better definition of the low to moderately contaminated locations by picking up small differences in anthropogenic metal concentrations. For the purposes of inter-regional comparison, we recommend a 4 h 1 M HCl acid extraction as a standard method for assessing metal contamination in Antarctica.     

Evaluation of geochemical methods for discrimination of metal contamination in Antarctic marine sediments: a case study from Casey Station

Detecting anthropogenic metal contamination in regional surveys can be particularly difficult when there is a lack of pre-disturbance data, especially when trying to differentiate low to moderate levels of contamination from background values. Furthermore, comparisons with other regional studies are confounded by differing analytical methods used and variations in sediment properties such as grainsize. Several types of geochemical technique, including weak acid partial extraction, strong acid extractions and total digestion have been used. Attempts have been made to overcome the influence that grainsize has on chemical concentrations in heterogeneous environments by analysing the fines, typically the mud fraction (<63 microm), in an attempt to improve the detection of anthropogenic contamination. Here we compare a weak acid partial extraction using 1M HCl and total digestion methods for a regional survey of reference and impacted sites in Antarctica using both whole sediment (<2 mm) and mud (<63 microm) fractions. The 1M partial extraction on whole sediment (<2 mm) most closely distinguished weakly, or moderately, impacted sites from reference locations. It also identified small scale within-location spatial variation in metal contamination that the total digest did not detect. Compared with total digests or analysis of the <63 microm fraction alone, this method minimised the possibility of a Type II statistical error in the regional survey - that is, failing to identify a site as being contaminated when it has elevated metal concentrations. To allow inter-regional comparison of sediment chemistry data from elsewhere in Antarctica, and also more generally, we recommend a 1M HCl partial extraction on whole sediment (<2 mm).