Ecological and water quality impairment resulting from the New Idria Mercury Mine and natural sources in the San Carlos and Silver Creek watersheds, central California

The New Idria Mercury Mine in central California is the second largest mercury (Hg) deposit in North America and has been proposed as a US EPA Superfund Site based on ecological impairment to the San Carlos and Silver Creek watersheds. Water, sediment, and biota were sampled in San Carlos Creek in the mine area and downstream for 25 km into the watershed termed Silver Creek. Release of acid rock drainage (ARD) and erosion of mine tailings have impacted the watershed during 120 years of mining and since the mine was closed in 1972. The watershed can be divided into three segments based on water and sediment composition, Hg sources and concentrations, and biodiversity of aquatic invertebrates. Creek waters in segment no. 1 above the mine area consist of Mg-Ca-CO3 meteoric water with pH 8.73. Hg concentrations are elevated in both sediment (100μg/g), and in waters (60 ng/L) because of erosion of Hg mine tailings in the upper part of the watershed. Invertebrate biodiversity is the highest of the sites sampled in the watershed, with seven families (six orders) of aquatic invertebrates collected and six other families observed. In the mine area isotopically heavy ARD (pH 2.7) with high levels of Fe(II), SO4, and total Hg (HgT: 76.7 ng/L) enters and mixes with meteoric creek water, constituting from 10-15% of the water in the 10-km long second creek segment downstream from the mine. Oxidation of Fe(II) from ARD results in precipitation of FeOOH which is transported and deposited as an Fe precipitate that has high Hg and MMeHg concentration (Hg: 15.7-79 μg/g, MMeHg: 0.31 - 1.06 ng/g). Concentrations of HgT are uniformly high (1530-2890 ng/L) with particulate Hg predominant. MMeHg ranges from 0.21-0.99 ng/L. In the area just downstream from the ARD source, biodiversity of invertebrates was low, with only one taxa (water striders) available in sufficient numbers and mass (> 1 g)_to be sampled. Biodiversity further downstream was also low, with only up to 2 families present at each site. In the third segment of the watershed, from 10 to 25 km downstream, water chemistry changes due to an input of isotopically heavy connate groundwater with elevated SO4, Cl, CO3, Ba, Ca, Ti, and Hg. HgT concentrations decrease systematically downstream from 680 to 20 ng/L. In the dry season, phytoplankton blooms in this segment of the creek result in accumulation of biogenic sediment up to 0.25 m thick that is composed of diatoms and chemically precipitated CaCO3. The tan surface layer consists of living diatoms. Below it is a black sediment composed of diatom fragments and micron to submicron size grains of FeS, HgS, and barite. Phytoplankton has high Hg and MMeHg bioaccumulation factors which results in high levels of Hg in the biogenic sediment. The expired diatoms release Hg to the pore waters of the sediment that reacts with sulfide generated by sulfate reducing bacteria and is precipitated as HgS. The Hg enriched biogenic sediment (4.5-14.4 μg/g) is a natural source of HgS to the watershed. In this creek segment, biodiversity is variable depending on riparian and in-stream habitat. The number of aquatic invertebrates present in sufficient numbers and mass for collection and analysis ranged from 2 to 7.