Temporal variation and the effect of rainfall on metals flux from the historic Beatson mine, Prince William Sound, Alaska, USA

Abstract Several abandoned Cu mines are located along the shore of Prince William Sound, AK, where the effect of mining-related discharge upon shoreline ecosystems is unknown. To determine the magnitude of this effect at the former Beatson mine, the largest Cu mine in the region and a Besshi-type massive sulfide ore deposit, trace metal concentration and flux were measured in surface run-off from remnant, mineralized workings and waste. Samples were collected from seepage waters; a remnant glory hole which is now a pit lake; a braided stream draining an area of mineralized rock, underground mine workings, and waste piles; and a background location upstream of the mine workings and mineralized rock. In the background stream pH averaged ∼7.3, specific conductivity (SC) was ∼40 μS/cm, and the aqueous components indicative of sulfide mineral weathering, SO4 and trace metals, were at detection limits or lower. In the braided stream below the mine workings and waste piles, pH usually varied from 6.7 to 7.1, SC varied from 40 to 120 μS/cm, SO4 had maximum concentrations of 32 mg/L, and the trace metals Cu, Ni, Pb, and Zn showed maximum total acid extractable concentrations of 186, 5.9, 6.2 and 343 μg/L, respectively. With an annual rainfall of ∼340 cm (estimated from the 2006 water year) it was expected that rain water would have a large effect on the chemistry of the braided stream draining the mine site. A linear mixing model with two end members, seepage water from mineralized rock and background water, estimated that the braided stream contained 10–35% mine drainage. After rain events the braided stream showed a decrease in pH, SC, Ca + Mg, SO4, and alkalinity, due to dilution. The trace metals Ni and Zn followed this same pattern. Sodium + K and Cl did not vary between the background and braided stream, nor did they vary with rainfall. At approximately 2 and 3 mg/L, respectively, these concentrations are similar to concentrations found in rainfall on the coasts of North America. High concentrations of total acid extractable Al and Fe were found at near-neutral pH in most of the waters collected at the site. Equilibrium solubility simulations, performed with PHREEQC, show that the stream waters are saturated with respect to Al, Fe and SiO2 solid phases. Because the “dissolved” sample fractions (acid preserved and filtered to 0.45 μm) show significant concentrations of Al and Fe it is presumed that these are present as colloids. The relationship between concentrations of Al and Fe, and rainfall was the opposite of that observed for the major ions Ca + Mg, SO4, and alkalinity, in that Al and Fe concentrations increased with increasing rainfall. Concentrations of Cu and Pb followed the same pattern. Adsorption calculations were performed with Visual MINTEQ, using the diffuse double layer electrostatic model and surface complexation constants for the ferrihydrite surface. These results suggest that 30–93% of Cu and 58–97% of Pb was adsorbed to ferrihydrite precipitates in the stream waters. Ni and Zn showed little adsorption in this pH range. Flux calculations show that the total mass of trace metals transported from the mine site, during the 60 day study period, was ranked as Zn (196 kg) > Cu (87 kg) > Pb(1.9 kg) ≈ Ni(1.9 kg). Nickel and Zn were transported mostly as dissolved species while Cu and Pb were transported mostly as adsorbed species. pH control on adsorption was evident when Cu and Pb isotherms were normalized by ferrihydrite flux. Decreased stream water pH due to periods of frequent and high volume rain events would cause desorption of Cu and Pb from the ferrihydrite surface, thus changing not only their speciation in solution but also their mechanism of transport.