Lanthanum, cerium, praseodymium and yttrium in waters in an upland acidic and acid sensitive environment, mid-Wales

Abstract. The less than 0.45 mm filterable lanthanum (La), cerium (Ce), praseodymium (Pr) and yttrium (Y) concentrations in rainfall, cloud water, stream and groundwater in the upper River Severn catchments of mid-Wales are presented, based on up to ten years of weekly data. Results show that for rainfall, there is enrichment in the rare earth (RE) elements, especially under conditions of small volume of catch. However, within the correlations, there is a 'forked' relationship, with one line of high La, Ce and Pr with low Y, corresponding to clear pollutant events and the other with relatively low La, Ce and Pr and higher Y to background conditions. Cloud water and stream waters show a simpler relationship indicating two types of source. Cloud, stream and ground water show no split in pattern, with singular linear relationships between the rare La, Ce, Pr and Y. However, in many cases the monitoring of the streams and groundwaters post-dates the rainfall period with high pollutant Ce inputs. RE element concentrations vary systematically, in general decreasing with increasing volume of catch for cloud-water. For the streams, occasionally, there are relatively high Ce and La concentrations (up to about a tenth the maximum in rainfall), which occur in the same year as the corresponding high values in rainfall. Apart from these anomalous periods, RE element concentrations increase with decreasing pH and increasing aluminium concentrations; RE elements are mobilised under acidic conditions. The river waters are particularly enriched in Y relative to La, Ce and Pr, both in terms of average concentrations and values normalised to standard continental shales. The RE element level in the streams is variable and seems to be linked to the main soil types within the catchment; gleys in particular show higher concentrations than their peat and podzolic counterparts. On average, groundwaters are enriched in the RE elements relative to the stream but the link with pH and aluminium observed in the stream is much weaker.