Metals in bulk deposition and surface waters at two upland locations in northern England.

Concentrations of aluminium and minor metals (Mn, Ni, Cu, Zn, Sr, Cd, Ba, Pb) were measured in precipitation and surface water at two upland locations (Upper Duddon Valley, UDV; Great Dun Fell, GDF) in northern England for 1 year commencing April 1998. At both locations, the loads in bulk precipitation were at the lower ends of ranges reported for other rural and remote sites, for the period 1985-1995. The deposited metals were mostly in the dissolved form, and their concentrations tended to be greatest when rainfall volumes were low. The concentrations of Cu, Zn and Pb in deposition were correlated (r2 > or = 0.40) with concentrations of non-marine sulphate. Three streams, ranging in mean pH from 5.07 to 7.07, and with mean concentrations of dissolved organic carbon (DOC) < 1 mg l(-1). were monitored at UDV, and two pools (mean pH 4.89 and 6.83, mean DOC 22 and 15 mg l(-1)) at GDF. Aluminium and the minor metals were mainly in the dissolved form, and in the following ranges (means of 49-51 samples. microg l(-1)): Al 36-530. Mn 4.4-36, Ni 0.26-2.8, Cu 0.25-1.7, Zn 2.1-30, Cd 0.03-0.16, Ba 1.9-140, Pb 0.10-4.5. Concentrations were generally higher at GDF. Differences in metal concentrations between the two locations and between waters at each location, and temporal variations in individual waters, can be explained qualitatively in terms of sorption to solid-phase soil organic matter and mineral surfaces, complexation and transport by DOC, and chemical weathering. The UDV catchments are sinks for Pb and sources of Al, Mn, Sr, Cd and Ba. The GDF catchments are sources of Al, Mn, Ni, Zn, Sr, Cd and Ba. Other metals measured at the two locations are approximately in balance. Comparison of metal:silicon ratios in the surface waters with values for silicate rocks indicates enrichment of Ni and Cu, and substantial enrichment of Zn, Cd and Pb. These enrichments, together with high metal deposition in the past, make it likely that concentrations of the metals in the surface waters are governed by release from catchment pools of atmospherically-deposited metal. The catchments appear to be responding on a time scale of decades, possibly centuries, to changes in metal deposition. For the more acid waters at UDV, the calculated free-ion concentrations of Al are similar to published LC50 values for acute toxicity towards fish. The free-ion concentrations of Ni, Cu, Zn and Cd in all the surface waters are one-to-four orders of magnitude lower than reported LC50 values for fish.