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L.L. Stillings

Publications and source records attributed to L.L. Stillings.

8 recordsLinked to original sources
USGS2014

Soil-plant-microbial relations in hydrothermally altered soils of Northern California

Soils developed on relict hydrothermally altered soils throughout the Western USA present unique opportunities to study the role of geology on above and belowground biotic activity and composition. Soil and vegetation samples were taken at three unaltered andesite and three hydrothermally altered (acid-sulfate) sites located in and around Lassen VolcanicNational Park in northeastern California. In addition, three different types of disturbed areas (clearcut, thinned, and pipeline) were sampled in acid-sulfate altered sites. Soils were sampled (0–15 cm) in mid-summer 2010 from both under-canopy and between-canopy areas within each of the sites. Soils were analyzed for numerous physical and chemical properties along with soil enzyme assays, C and N mineralization potential, microbial biomass-C and C-substrate utilization. Field vegetation measurements consisted of canopy cover by life form (tree, shrub, forb, and grass), tree and shrub density, and above-ground net primary productivity of the understory. Overall, parameters at the clearcut sites were more similar to the unaltered sites, while parameters at the thinned and pipeline sites were more similar to the altered sites. We employed principal components analysis (PCA) to develop two soil quality indices (SQI) to help quantify the differences among the sites: one based on the correlation between soil parameters and canopy cover, and the second based on six sub-indices. Soil quality indices developed in these systems could provide a means for monitoring and identifying key relations between the vegetation, soils, and microorganisms.

California↗
USGS2011

Biogeochemical factors affecting the presence of 210 Po in groundwater

The discovery of natural 210 Po enrichment at levels exceeding 500 mBq/L in numerous domestic wells in northern Nevada, USA, led to a geochemical investigation of the processes responsible for its mobilization. 210 Po activities in 63 domestic and public-supply wells ranged from below 1 mBq/L to 6590 ± 590 mBq/L, among the highest reported levels in the USA. There is little spatial or depth variability in 210Pb activity in study-area sediments and mobilization of a few percent of the 210 Po in the sediments would account for all of the 210 Po in water. Stable-isotope measurements indicate SO 4 reduction has occurred in all 210 Po contaminated wells. Sulfide species are not accumulating in the groundwater in much of Lahontan Valley, probably because of S cycling involving microbial SO 4 reduction, abiotic oxidation of H 2 S to S 0 by Mn(IV), followed by microbial disproportionation of S 0 to H 2 S and SO 4 . The high pH, Ca depletion, MnCO3 saturation, and presence of S 0 in Lahontan Valley groundwater may be consequences of the anaerobic S cycling. Consistent with data from naturally-enriched wells in Florida, 210 Po activities begin to decrease when aqueous sulfide species begin to accumulate. This may be due to formation and precipitation of PoS, however, Eh–pH diagrams suggest PoS would not be stable in study-area groundwater. An alternative explanation for the study area is that H 2 S accumulation begins when anaerobic S cycling stops because Mn oxides are depleted and their reduction is no longer releasing 210 Po. Common features of 210 Po-enriched groundwater were identified by comparing the radiological and geochemical data from Nevada with data from naturally-enriched wells in Finland, and Florida and Maryland in the USA. Values of pH ranged from <5 in Florida wells to >9 in Nevada wells, indicating that pH is not critical in determining whether 210 Po is present. Where U is present in the sediments, the data suggest 210 Po levels may be elevated in aquifers with (1) SO 4 -reducing waters with low H 2 S concentrations, or (2) anoxic or oxic waters with extremely high Rn activities, particularly if the water is turbid.

Applied Geochemistry↗
USGS2008

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↗
USGS2008

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↗
USGS2006

Modeling spatial and temporal variations in temperature and salinity during stratification and overturn in Dexter Pit Lake, Tuscarora, Nevada, USA

This paper examines the seasonal cycling of temperature and salinity in Dexter pit lake in arid northern Nevada, and describes an approach for modeling the physical processes that operate in such systems. The pit lake contains about 596,200 m 3 of dilute, near neutral (pHs 6.7–9) water. Profiles of temperature, conductivity, and selected element concentrations were measured almost monthly during 1999 and 2000. In winter (January–March), the pit lake was covered with ice and bottom water was warmer (5.3 °C) with higher total dissolved solids (0.298 g/L) than overlying water (3.96 °C and 0.241 g/L), suggesting inflow of warm (11.7 °C) groundwater with a higher conductivity than the lake (657 versus 126–383 μS/cm). Seasonal surface inflow due to spring snowmelt resulted in lower conductivity in the surface water (232–247 μS/cm) relative to deeper water (315–318 μS/cm). The pit lake was thermally stratified from late spring through early fall, and the water column turned over in late November (2000) or early December (1999). The pit lake is a mixture of inflowing surface water and groundwater that has subsequently been evapoconcentrated in the arid environment. Linear relationships between conductivity and major and some minor (B, Li, Sr, and U) ions indicate conservative mixing for these elements.

Nevada↗
USGS1998

Oxalate adsorption at a plagioclase (An47) surface and models for ligand-promoted dissolution

Previous work on adsorption of oxalate at aluminosilicate surfaces suggests that maximum adsorption occurs through a bidentate attachment of the organic ligand, at near-neutral pH. Rates of ligand-promoted dissolution are expected to be greatest at this pH as well. We tested this model by measuring oxalate adsorption on the surface of andesine (An47), in solutions of pH 3- 5 and total oxalate concentrations of 0-8 mM. Contrary to expectation, the greatest adsorption density of 24 ??mol m-2 total oxalate was observed at pH 3 and 8 mM total oxalate. Adsorption is dependent upon the activities of both oxalate (C2O42-) and bioxalate (HC2O4-) in solution and can be modeled with either a two-term Langmuir or a two-term Freundlich isotherm. A Freundlich adsorption model provided the best fit to rate data because it was not constrained to a finite number of adsorption sites, as was the Langmuir model. The two-term ligand adsorption model was incorporated into a rate model: R(tot) = k(H-)[H(ads)/+](L) + k(HOx-)[HOx(ads)/-] + k(Ox2- )[Ox2(ads)/-] where R(tot) is the net dissolution rate of the feldspar, [i(ads)] is the concentration of species i adsorbed to the surface, and k(i) is the rate constant for release of the surface complex. The model was fit to data for oxalate-promoted dissolution of andesine, resulting in estimates for the rate constants of k(HOx-) = 1.16 x 10-12, k(Ox2-) = 1.05 x 10-12, and k(H-) = 9.61 x 10-13 mol of feldspar (??mol of i) (??mol of i)-1 s-1.Previous work on adsorption of oxalate at aluminosilicate surfaces suggests that maximum adsorption occurs through a bidentate attachment of the organic ligand, at near-neutral pH. Rates of ligand-promoted dissolution are expected to be greatest at this pH as well. We tested this model by measuring oxalate adsorption on the surface of andesine (An47), in solutions of pH 3-5 and total oxalate concentrations of 0-8 mM. Contrary to expectation, the greatest adsorption density of 24 ??mol m-2 total oxalate was observed at pH 3 and 8 mM total oxalate. Adsorption is dependent upon the activities of both oxalate (C2O42-) and bioxalate (HC2O4-) in solution and can be modeled with either a two-term Langmuir or a two-term Freundlich isotherm. A Freundlich adsorption model provided the best fit to rate data because it was not constrained to a finite number of adsorption sites, as was the Langmuir model. The two-term ligand adsorption model was incorporated into a rate model: Rtot = kH(+)[Hads+]L +kHOx(-) [HOxads-]+kOx(2-) [Oxads 2-] where Rtot is the net dissolution rate of the feldspar, [iads] is the concentration of species i adsorbed to the surface, and ki is the rate constant for release of the surface complex. The model was fit to data for oxalate-promoted dissolution of andesine, resulting in estimates for the rate constants of kHOx(-) = 1.16??10-12, kOx(2-) = 1.05??10-12, and kH(+) = 9.61??10-13 mol of feldspar (??mol of i)-1 s-1.

Environmental Science & Technology↗