Dynamic modelling of atmospherically-deposited Ni, Cu, Zn, Cd and Pb in Pennine catchments (northern England).

Simulation modelling with CHUM-AM was carried out to investigate the accumulation and release of atmospherically-deposited heavy metals (Ni, Cu, Zn, Cd and Pb) in six moorland catchments, five with organic-rich soils, one with calcareous brown earths, in the Pennine chain of northern England. The model considers two soil layers and a third layer of weathering mineral matter, and operates on a yearly timestep, driven by deposition scenarios covering the period 1400-2010. The principal processes controlling heavy metals are competitive solid-solution partitioning of solutes, chemical interactions in solution, and chemical weathering. Agreement between observed and simulated soil metal pools and surface water concentrations for recent years was generally satisfactory, the results confirming that most contemporary soil metal is from atmospheric pollution. Metals in catchments with organic-rich soils show some mobility, especially under more acid conditions, but the calcareous mineral soils have retained nearly all anthropogenic metal inputs. Complexation by dissolved organic matter and co-transport accounts for up to 80% of the Cu in surface waters.

Reconstructing temporal trends in heavy metal deposition: assessing the value of herbarium moss samples.

The use of the herbarium moss archive for investigating past atmospheric deposition of Ni, Cu, Zn, As, Cd and Pb was evaluated. Moss samples from five UK regions collected over 150 years were analysed for 26 elements using ICP-MS. Principal components analysis identified soil as a significant source of Ni and As and atmospheric deposition as the main source of Pb and Cu. Sources of Zn and Cd concentrations were identified to be at least partly atmospheric, but require further investigation. Temporal and spatial trends in metal concentrations in herbarium mosses showed that the highest Pb and Cu levels are found in Northern England in the late 19th century. Metal concentrations in herbarium moss samples were consistently higher than those in mosses collected from the field in 2000. Herbarium moss samples are concluded to be a useful resource to contribute to reconstructing trends in Pb and Cu deposition, but not, without further analysis, for Cd, Zn, As and Ni.

Simulating the long-term chemistry of an upland UK catchment: heavy metals.

CHUM-AM was used to investigate the behaviours of atmospherically-deposited heavy metals (Ni, Cu, Zn, Cd and Pb) in three moorland sub-catchments in Cumbria UK. The principal processes controlling cationic metals are competitive partitioning to soil organic matter, chemical interactions in solution, and chemical weathering. Metal deposition histories were generated by combining measured data for the last 30 years with local lake sediment records. For Ni, Cu, Zn and Cd, default parameters for the interactions with organic matter provided reasonable agreement between simulated and observed present-day soil metal pools and average streamwater concentrations. However, for Pb, the soil binding affinity in the model had to be increased to match the observations. Simulations suggest that weakly-sorbing metals (Ni, Zn, Cd) will respond on timescales of decades to centuries to changes in metal inputs or acidification status. More strongly-sorbing metals (Cu, Pb) will respond over centuries to millennia.