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Aaron J. Slowey

Publications and source records attributed to Aaron J. Slowey.

4 recordsLinked to original sources

How to overcome inter-electrode variability and instability to quantify dissolved oxygen, Fe(II), mn(II), and S(−II) in undisturbed soils and sediments using voltammetry

Background - Although uniquely capable of measuring multiple redox constituents nearly simultaneously with no or minimal sample pretreatment, voltammetry is currently underutilized in characterizing redox conditions in aquatic and terrestrial systems. Investigation of undisturbed media such as pore water requires a solid-state electrode, and such electrodes can be difficult to fabricate reproducibly. An approach to determine the concentrations of electroactive constituents using indirectly calibrated electrodes has been developed, but the protocol for and accuracy of this approach—the pilot ion method—has not been documented in detail. Results - A detailed procedure for testing electrode quality is provided, and the application and limitations of the pilot ion method have been documented. To quantify Fe(II) and Mn(II), subtraction of non-linear baseline functions from voltammetric signals produced better calibration curves than did linear baselines, enabled lower detection limits and reliable deconvolution of overlapping signals, and was successfully applied to sediment pore water signals. We observed that electrode sensitivities often vary by tens of percent, and that the sensitivity declines over time. The ratio of calibration slopes of Mn(II) to Fe(II) varied by no more than 11% from one Hg/Au electrode to another and Fe(II) concentrations predicted by the Mn(II) pilot ion were, on average, 13% different from their actual values. However, concentration predictions by the pilot ion method were worse for less than 15 μM Fe(II) (46% different on average). The ratio of calibration slopes of Mn(II) to S(−II) varied by almost 20% from one Hg/Au electrode to another, and S(−II) predicted concentrations were as much as 58% different from their actual values. These predictions of Fe(II) and S(−II) concentrations indicate that the accuracy of the pilot ion method depends on how independent calibration slope ratios are from the electrode used. At medium-to-high concentration for the ocean, naturally derived dissolved organic carbon did not significantly affect the baseline-corrected electrode response of Mn(II) and Fe(II), but did significantly affect the response of S(−II). Conclusions - Despite their intrinsic variability, Hg/Au electrodes fabricated by hand can be used to quantify O2, S(−II), Fe(II), and Mn(II) without calibrating every electrode for every constituent of interest. The pilot ion method can achieve accuracies to within 20% or less, provided that the underlying principle—the independence of slope ratios—is demonstrated for all voltammetric techniques used, and effects of the physicochemical properties of the system on voltammetric signals are addressed through baseline subtraction.

Geochemical Transactions

Rate of formation and dissolution of mercury sulfide nanoparticles: The dual role of natural organic matter

Mercury is a global contaminant of concern due to its transformation by microorganisms to form methylmercury, a toxic species that accumulates in biological tissues. The effect of dissolved organic matter (DOM) isolated from natural waters on reactions between mercury(II) (Hg) and sulfide (S(-II)) to form HgS (s) nanoparticles across a range of Hg and S(-II) concentrations was investigated. Hg was equilibrated with DOM, after which S(-II) was added. Dissolved Hg (Hg aq ) was periodically quantified using ultracentrifugation and chemical analysis following the addition of S(-II). Particle size and identity were determined using dynamic light scattering and X-ray absorption spectroscopy. S(-II) reacts with Hg to form 20 to 200nm aggregates consisting of 1-2 nm HgS (s) subunits that are more structurally disordered than metacinnabar in the presence of 2 x 10 -9 to 8 x 10 -6 M Hg and 10 (mg C)L -1 DOM. Some of the HgS(s) nanoparticle aggregates are subsequently dissolved by DOM and (re)precipitated by S(-II) over periods of hours to days. At least three fractions of Hg-DOM species were observed with respect to reactivity toward S(-II): 0.3 μmol reactive Hg per mmol C (60 percent), 0.1 μmol per mmol C (20 percent) that are kinetically hindered, and another 0.1 μmol Hg per mmol C (20 percent) that are inert to reaction with S(-II). Following an initial S(-II)-driven precipitation of HgS (s) , HgS (s) was dissolved by DOM or organic sulfur compounds. HgS (s) formation during this second phase was counterintuitively favored by lower S(-II) concentrations, suggesting surface association of DOM moieties that are less capable of dissolving HgS (s) . DOM partially inhibits HgS(s) formation and mediates reactions between Hg and S(-II) such that HgS (s) is susceptible to dissolution. These findings indicate that Hg accessibility to microorganisms could be controlled by kinetic (intermediate) species in the presence of S(-II) and DOM, undermining the premise that equilibrium Hg species distributions should correlate to the extent or rate of Hg methylation in soils and sediments.

Geochimica et Cosmochimica Acta

Mercury Release from the Rathburn Mine, Petray Mine, and Bear Valley Saline Springs, Colusa County, California 2004-2006

This report summarizes data obtained from field sampling of mine tailings and waste rock at the Rathburn and Petray Mines that was initiated in July 17, 2001 and water and sediment in regional springs and tributaries that drain from the mine area into Bear Creek on December 14, 2004 and February 16 and May 27, 2005. Although it was initially assumed that the mines were the cause of elevated levels of monomethyl Hg measured by the Central Regional Water Quality Control Board in tributaries near their confluence with Bear Creek (Foe and others, unpublished results), it became apparent during this study that ground water springs were also potential sources of Hg. In addition to sampling of springs in May 2005, saline ground water seepage along an unnamed fault on the west side of Bear Valley was sampled on December 13-14, 2006. We did not sample water or sediment in Bear Creek itself during this study. Our results permit a preliminary assessment of mining and natural sources of Hg and associated chemical constituents that could elevate levels of monomethyl Hg in Bear Creek.

Open-File Report

Mercury at the Oat Hill Extension Mine and James Creek, Napa County, California: Tailings, sediment, water, and biota, 2003-2004

The Oat Hill Extension (OHE) Mine is one of several mercury mines located in the James Creek/Pope Creek watershed that produced mercury from the 1870's until 1944 (U.S. Bureau of Mines, 1965). The OHE Mine developed veins and mineralized fault zones hosted in sandstone that extended eastward from the Oat Hill Mine. Waste material from the Oat Hill Mine was reprocessed at the OHE Mine using gravity separation methods to obtain cinnabar concentrates that were processed in a retort. The U.S. Bureau of Land Management requested that the U.S. Geological Survey measure and characterize mercury and other chemical constituents that are potentially relevant to ecological impairment of biota in tailings, sediment, and water at the OHE Mine and in the tributaries of James Creek that drain the mine area (termed Drainage A and B ) (Figs. 1 and 2). This report summarizes such data obtained from sampling of tailings and sediments at the OHE on October 17, 2003; water, sediment, and biota from James Creek on May 20, 2004; and biota on October 29, 2004. These data are interpreted to provide a preliminary assessment of the potential ecological impact of the mine on the James Creek watershed. The mine tailings are unusual in that they have not been roasted and contain relatively high concentrations of mercury (400 to 1200 ppm) compared to unroasted waste rock at other mines. These tailings have contaminated a tributary to James Creek with mercury primarily by erosion, on the basis of higher concentration of mercury (780 ng/L) measured in unfiltered (total mercury, Hg T ) spring water flowing from the OHE to James Creek compared to 5 to 14 ng/L Hg T measured in James Creek itself. Tailing piles (presumably from past Oat Hill mine dumping) near the USBLM property boundary and upstream of the main OHE mine drainage channel ( Drainage A ; Fig. 2) also likely emit mercury, on the basis of their mercury composition (930 to 1200 ppm). The OHE spring water is likely an appreciable source of sulfate and carbonate to James Creek, because the spring water was enriched in sulfate (130 mg/L) and carbonate (430 mg/L as CaCO 3 ) compared to James Creek water (70 to 100 mg/L SO 4 2- and 110 to 170 mg/L as CaCO 3 ) at the time of sampling. Concentrations of mercury in active channel sediment from James Creek are variable and potentially high, on the basis of chemical analysis (2.5 to 17 _g/g-wet sediment) and easily visible cinnabar grains in panned concentrates. Average (geometric mean) organic mercury (presumably monomethyl mercury (MMHg); §2.3.3) concentrations in several invertebrate taxa collected from the James Creek watershed locations were higher than invertebrates taken from a Northern California location lacking a known point source of mercury. The mean proportion of MMHg to total mercury in James Creek predatory insect samples was 40 percent (1 standard deviation = 30 percent); only 40 percent of all insect samples had a MMHg/Hg T proportion greater than 0.5. The low proportions of MMHg measured in invertebrates in James Creek and the presence of cinnabar in the creek suggest that some invertebrates may have anomolously high Hg concentrations as a result of the injestion or adhesion of extremely fine-grained cinnabar particles. Interpretation of Hg T in frogs and fish as an indicator of mercury reactivity, biouptake, or trophic transfer is limited, pending MMHg measuremens, by the possibility of these whole-body samples having contained cinnabar particles at the time of analysis. To minimize this limitation, the gastrointestinal tracts and external surfaces of all amphibians, where cinnabar most likely resides, were carefully flushed to remove any visible particles. However, extremely fine-grained, invisible, adhesive cinnabar particles likely exist in the amphibians' habitats. Hg T in foothill yellow-legged frogs collected from the James Creek study area, ranging from 0.1 to 0.6 μg/g Hg, was on average twice that of an extensive database compiled from Hg T in frogs studied throughout Northern California. Average concentrations of Hg T in frogs from James Creek were similar upstream (0.18 μg/g) and downstream (0.15 μg/g) of the confluence with Tributary 1 and at the lower Corona Mine adit drainage (0.14 μg/g). Frogs may be susceptible to trophic transfer of MMHg from invertebrates, but further study is required to rule out cinnabar ‘contamination.’ Hg T concentrations in rainbow trout collected from James Creek upstream and downstream of Tributary 1 averaged 0.10 μg/g and 0.13 μg/g, respectively. Compared to invertebrates, trout Hg T was less variable, suggesting that trout were less contaminated with cinnabar. California roach had significantly higher Hg T on average than trout (0.16 vs. 0.12 μg/g), and can be considered moderately contaminated compared to the same species from other sites in Northern California, which average 0.12 μg/g Hg. While limited measurements of mercury in water, sediment, and fish exceed, in some samples, predefined ecologically protective criteria for mine-impacted California systems, they do not clearly demonstrate that the biota residing in James Creek in the vicinity of the OHE are ecologically impaired. The potential for ecological impairment is clearly evident from invertebrate methyl mercury results and may manifest in other biological ecosystem residents that have yet to be studied (e.g., piscivorous birds). Methyl mercury concentrations in flowing water and sediment from James Creek and the tributary that drains the OHE are relatively low, ranging from 0.04 to 0.08 ng/L, although these data should be cautiously interpreted (see §3.2). While the results of this investigation suggest that the OHE contributes inorganic mercury to James Creek, they do not indicate the extent to which the OHE site is ecologically impairing biota relative to other sources of mercury. Improved sampling and analytical methods are recommended for future study.

California