Occurrence and fate of corrosion-induced zinc in runoff water from external structures.

This paper comprises data from an extensive cross-disciplinary research project aiming to elucidate the environmental fate of corrosion-induced zinc release from external structures. It includes an exposure assessment that provide long-term runoff rates, concentrations and chemical speciation of zinc, from 14 zinc-based materials exposed during 5 years in Stockholm, Sweden, and an effect assessment including bioavailability and ecotoxicity measurements, both at the immediate release situation and after soil interaction. Runoff rates of total zinc ranged from 0.07 to 2.5 g Znm-2 yr-1 with zinc primarily released as the free ion for all materials investigated. The average effect concentration, causing a 50% growth reduction after 72 h to the green algae Raphidocelis subcapitata, was at the immediate release situation 69 microg ZnL-1. Upon interaction of runoff water with soil, which simulated 18 to 34 years of exposure, the total zinc concentration was significantly reduced, from milligram per litre to microgram per litre levels. Simultaneously, the most bioavailable fraction of zinc in runoff, the hydrated zinc(II)-ion, decreased from more than 95% to about 30%. The major fraction, 98-99%, of the introduced total zinc concentration in the runoff water was retained within the soil. As long as the soil retention capacity was not reached, this resulted in zinc concentrations in the percolate water transported through the soil layer, close to background values and below growth inhibition concentrations for the green algae investigated. Zinc retained in soil was to a large extent (85-99.9%) extractable with EDTA, and available for plant uptake after 5 to 7 months of ageing.

Model studies of corrosion-induced copper runoff fate in soil.

Laboratory experiments have been performed with 3-cm soil columns simulating the fate of corrosion-induced copper runoff in contact with soil. The investigation simulates approximately 30 years (assuming an infiltration surplus of 25 cm/year) of continuous percolation of copper containing runoff water of a concentration realistic at the immediate release situation (4.8 mg/L) into four soils representative of urban conditions. Two of the three investigated topsoils reached their breakthrough of copper within the simulated time, while the third topsoil did not show a breakthrough. The subsoil reached a breakthrough after approximately 10 years of simulated exposure. To simulate more realistic outdoor scenarios, the laboratory-obtained breakthrough curves were modeled with Hydrus-1D using a Langmuir-Freundlich model to describe copper sorption, the parameters of which were estimated from soil properties (pH, organic carbon content). The model predicts longer breakthrough times with increasing pH and organic content of the soil and with decreasing concentrations of copper and dissolved organic carbon in the runoff water. The time span for copper in runoff water (at concentrations of 0.01-10 mg/L) to reach a soil depth of 50 cm varied between 170 and more than 8,000 years for the predicted field scenarios.

Long-term corrosion-induced copper runoff from natural and artificial patina and its environmental impact.

The overall objective of this paper is to present an extensive set of data for corrosion-induced copper dispersion and its environmental interaction with solid surfaces in the near vicinity of buildings. Copper dispersion is discussed in terms of total copper flows, copper speciation and bioavailability at the immediate release situation, and its changes during transport from source to recipient. Presented results are based on extensive field exposures (eight years) at an urban site, laboratory investigations of the runoff process, published field data, generated predictive site-specific runoff rate models, and reactivity investigations toward various natural and manmade surfaces, such as those in soil, limestone, and concrete. Emphasis is placed on the interaction of copper-containing runoff water with different soil systems through long-term laboratory column investigations. The fate of copper is discussed in terms of copper retention, copper chemical speciation, breakthrough capacities, and future mobilization based on changes in copper concentrations in the percolate water, computer modeling using the Windermere Humic Aqueous Model, and sequential extractions. The results illustrate that, for scenarios where copper comes in extensive contact with solid surfaces, such as soil and limestone, a large fraction of released copper is retained already in the immediate vicinity of the building. In all, both the total copper concentration in runoff water and its bioavailable part undergo a significant and rapid reduction.

Predictive models of copper runoff from external structures.

A general model for annual runoff rate predictions of total copper from naturally patinated copper on buildings at specific urban or rural sites of low chloride influence has been deduced from laboratory and field data. All parameters within the model have a physical meaning and include the average annual rain acidity (pH), the annual rain quantity and the geometry of a building in terms of surface inclination. In 70% of all reported annual runoff rates, the predicted values are within 30% from the observed values. The individual and interactive effect of rain composition in terms of pH, sulfate, chloride and nitrate concentration was investigated in immersion experiments in artificial rain water representative of urban and rural sites of Europe. The results show pH to have a dominating effect on patina dissolution, nitrate to have a small inhibiting effect, whereas no significant effect was seen for chloride and sulfate. In case pH data are not available, a model has been statistically deduced from field data by considering SO2 as influencing parameter, rather than pH. The predictability with the SO2 model is not as good as with the pH model i.e. the pH model should preferentially be used since it is a better predictor and all parameters within the model can be physically explained.