Provenancing anthropogenic Pb within the fluvial environment: developments and challenges in the use of Pb isotopes

The potentially deleterious presence of ore-derived Pb within riverine environments has been a long-term impact of industrial and anthropogenic activity in general. The surface drainage network has been widely established as a key transport mechanism and storage environment for anthropogenically-derived Pb and other potentially harmful trace metals. Lead isotopes ((204)Pb, (206)Pb, (207)Pb, (208)Pb) have been utilized as a geochemical tracer of Pb origin in a variety of environmental media, notably in atmospheric aerosols. However, given the relative complexity of dispersal processes within riverine environments, the use of Pb isotopes as geochemical tracers has been relatively limited and it is only relatively recently that a growing body of research has applied Pb isotopes to provenancing fluvially-dispersed Pb. This paper seeks to synthesize the developments in the use of Pb isotopes within riverine environments. In doing so it outlines the Pb-isotope fingerprinting technique and associated analytical developments, and assesses the application of Pb isotopes in establishing the origin and dispersal mechanisms of anthropogenically- and geogenically-derived Pb at a range of temporal and spatial scales. Of particular importance are the approaches quantifying source inputs using Pb isotopic signatures and the challenges faced, and options available in quantifying source inputs at the catchment scale; where Pb may be sourced from a variety (n=>2) of sources. The Pb isotopic signature of contemporary riverine Pb loads is shown to reflect a spatially complex influence of mineralization chemistry, anthropogenic activity as well as the hydro-morphological controls exerted upon Pb release, dispersal and storage. In relation to this, the long-term environmental legacy, and its influence upon Pb fingerprinting studies, of tetra-ethyl Pb, sourced from the combustion of leaded-petrol is also discussed. Finally, this paper places the use of Pb isotopes in the context of recently developed Cu and Zn isotopic fingerprinting techniques and assesses the role of Pb, Cu and Zn isotopes in a multi-proxy approach to geochemical tracing.