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L. Munk

Publications and source records attributed to L. Munk.

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Sulfide oxidation and distribution of metals near abandoned copper mines in coastal environments, Prince William Sound, Alaska, USA

The oxidation of sulfide-rich rocks, mostly leftover debris from Cu mining in the early 20th century, is contributing to metal contamination of local coastal environments in Prince William Sound, Alaska. Analyses of sulfide, water, sediment, precipitate and biological samples from the Beatson, Ellamar, and Threeman mine sites show that acidic surface waters generated from sulfide weathering are pathways for redistribution of environmentally important elements into and beyond the intertidal zone at each site. Volcanogenic massive sulfide deposits composed of pyrrhotite and (or) pyrite + chalcopyrite + sphalerite with subordinate galena, arsenopyrite, and cobaltite represent potent sources of Cu, Zn, Pb, As, Co, Cd, and Hg. The resistance to oxidation among the major sulfides increases in the order pyrrhotite ??? sphalerite < chalcopyrite ??? pyrite; thus, pyrrhotite-rich rocks are typically more oxidized than those dominated by pyrite. The pervasive alteration of pyrrhotite begins with rim replacement by marcasite followed by replacement of the core by sulfur, Fe sulfate, and Fe-Al sulfate. The oxidation of chalcopyrite and pyrite involves an encroachment by colloform Fe oxyhydroxides at grain margins and along crosscutting cracks that gradually consumes the entire grain. The complete oxidation of sulfide-rich samples results in a porous aggregate of goethite, lepidocrocite and amorphous Fe-oxyhydroxide enclosing hydrothermal and sedimentary silicates. An inverse correlation between pH and metal concentrations is evident in water data from all three sites. Among all waters sampled, pore waters from Ellamar beach gravels have the lowest pH (???3) and highest concentrations of base metals (to ???25,000 ??g/L), which result from oxidation of abundant sulfide-rich debris in the sediment. High levels of dissolved Hg (to 4100 ng/L) in the pore waters probably result from oxidation of sphalerite-rich rocks. The low-pH and high concentrations of dissolved Fe, Al, and SO4 are conducive to precipitation of interstitial jarosite in the intertidal gravels. Although pore waters from the intertidal zone at the Threeman mine site have circumneutral pH values, small amounts of dissolved Fe2+ in the pore waters are oxidized during mixing with seawater, resulting in precipitation of Fe-oxyhydroxide flocs along the beach-seawater interface. At the Beatson site, surface waters funneled through the underground mine workings and discharged across the waste dumps have near-neutral pH (6.7-7.3) and a relatively small base-metal load; however, these streams probably play a role in the physical transport of metalliferous particulates into intertidal and offshore areas during storm events. Somewhat more acidic fluids, to pH 5.3, occur in stagnant seeps and small streams emerging from the Beatson waste dumps. Amorphous Fe precipitates in stagnant waters at Beatson have high Cu (5.2 wt%) and Zn (2.3 wt%) concentrations that probably reflect adsorption onto the extremely high surface area of colloidal particles. Conversely, crystalline precipitates composed of ferrihydrite and schwertmannite that formed in the active flow of small streams have lower metal contents, which are attributed to their smaller surface area and, therefore, fewer reactive sorption sites. Seeps containing precipitates with high metal contents may contribute contaminants to the marine environment during storm-induced periods of high runoff. Preliminary chemical data for mussels (Mytilus edulis) collected from Beatson, Ellamar, and Threeman indicate that bioaccumulation of base metals is occurring in the marine environment at all three sites.

Applied Geochemistry↗

Relationships between microbial communities and environmental parameters at sites impacted by mining of volcanogenic massive sulfide deposits, Prince William Sound, Alaska

The relations among geochemical parameters and sediment microbial communities were examined at three shoreline sites in the Prince William Sound, Alaska, which display varying degrees of impact by acid-rock drainage (ARD) associated with historic mining of volcanogenic massive sulfide deposits. Microbial communities were examined using total fatty acid methyl esters (FAMEs), a class of compounds derived from lipids produced by eukaryotes and prokaryotes (bacteria and Archaea); standard extraction techniques detect FAMEs from both living (viable) and dead (non-viable) biomass, but do not detect Archaeal FAMEs. Biomass and diversity (as estimated by FAMEs) varied strongly as a function of position in the tidal zone, not by study site; subtidal muds, Fe oxyhydroxide undergoing biogenic reductive dissolution, and peat-rich intertidal sediment had the highest values. These estimates were lowest in acid-generating, intertidal zone sediment; if valid, the estimates suggest that only one or two bacterial species predominate in these communities, and/or that Archeal species are important members of the microbial community in this sediment. All samples were dominated by bacterial FAMEs (median value >90%). Samples with the highest absolute abundance of eukaryotic FAMEs were biogenic Fe oxyhydroxides from shallow freshwater pools (fungi) and subtidal muds (diatoms). Eukaryotic FAMEs were practically absent from low-pH, sulfide-rich intertidal zone sediments. The relative abundance of general microbial functional groups such as aerobes/anaerobes and gram(+)/gram(-) was not estimated due to severe inconsistency among the results obtained using several metrics reported in the literature. Principal component analyses (PCAs) were performed to investigate the relationship among samples as separate functions of water, sediment, and FAMEs data. PCAs based on water chemistry and FAMEs data resulted in similar relations among samples, whereas the PCA based on sediment chemistry produced a very different sample arrangement. Specifically, the sediment parameter PCA grouped samples with high bulk trace metal concentration regardless of whether the metals were incorporated into secondary precipitates or primary sulfides. The water chemistry PCA and FAMEs PCA appear to be less prone to this type of artifact. Signature lipids in sulfide-rich sediments could indicate the presence of acid-tolerant and/or acidophilic members of the genus Thiobacillus or they could indicate the presence of SO4-reducing bacteria. The microbial community documented in subtidal and offshore sediments is rich in SRB and/or facultative anaerobes of the Cytophaga-Flavobacterium group; both could reasonably be expected in PWS coastal environments. The results of this study provide evidence for substantial feedback between local (meter to centimeter-scale) geochemical variations, and sediment microbial community composition, and show that microbial community signatures in the intertidal zone are significantly altered at sites where ARD drainage is present relative to sites where it is not, even if the sediment geochemistry indicates net accumulation of ARD-generated trace metals in the intertidal zone. ?? 2007 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

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

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 ??S/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 ??S/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 ??g/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 ??m) 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. ?? 2007 Elsevier Ltd. All rights reserved.

Applied Geochemistry↗

Geochemical evolution of solutions derived from experimental weathering of sulfide-bearing rocks

The chemical composition of natural waters is affected by the weathering of geologic materials at or near the surface of the Earth. Laboratory weathering experiments of whole-rock sulfide rocks from the Shoe-Basin Mine (SBM) and the Pennsylvania Mine (PM) from the Peru Creek Basin, Summit County, Colorado, indicate that the mineral composition of the sulfide rocks, changes in pH, the duration of the experiment, and the formation of sorbents such as Fe and Al oxyhydroxides affect the chemical composition of the resulting solution. Carbonate minerals in the rock from SBM provide buffering capacity to the solution, contribute to increases in the pH and enhance the formation of Fe and Al oxyhydroxides, which sorb cations from solution. The final solution pH obtained in the experiments was similar to those measured in the field (i.e., 2.8 for PM and 5.0 for SBM). At PM, acidic, metal-rich mine effluent is discharged into Peru Creek where it mixes with stream water. As a result, the pH of the effluent increases causing Fe and Al oxyhydroxide and schwertmannite to precipitate. The resulting solids sorb metal cations from the water thereby improving the quality of the water in Peru Creek. ?? 2006.

Applied Geochemistry↗