Geology topics

K.W. Mandernack

Publications and source records attributed to K.W. Mandernack.

8 recordsLinked to original sources

USGS2012

Oxygen and sulfur isotope systematics of sulfate produced during abiotic and bacterial oxidation of sphalerite and elemental sulfur

Studies of metal sulfide oxidation in acid mine drainage (AMD) systems have primarily focused on pyrite oxidation, although acid soluble sulfides (e.g., ZnS) are predominantly responsible for the release of toxic metals. We conducted a series of biological and abiotic laboratory oxidation experiments with pure and Fe-bearing sphalerite (ZnS & Zn 0.88 Fe 0.12 S), respectively, in order to better understand the effects of sulfide mineralogy and associated biogeochemical controls of oxidation on the resultant δ 34 S and δ 18 O values of the sulfate produced. The minerals were incubated in the presence and absence of Acidithiobacillus ferrooxidans at an initial solution pH of 3 and with water of varying δ 18 O values to determine the relative contributions of H 2 O-derived and O 2 -derived oxygen in the newly formed sulfate. . Experiments were conducted under aerobic and anaerobic conditions using O 2 and Fe(III) aq as the oxidants, respectively. Aerobic incubations with A. ferrooxidans , and S o as the sole energy source were also conducted. The δ 34 S SO 4 "> δ34SSO4 values from both the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq produced sulfur isotope fractionations ( ε 34 S SO 4 - ZnS "> ε34SSO4-ZnS ) of up to −2.6‰, suggesting the accumulation of sulfur intermediates during incomplete oxidation of the sulfide. No significant sulfur isotope fractionation was observed from any of the aerobic experiments. Negative sulfur isotope enrichment factors ( ε 34 S SO 4 - ZnS "> ε34SSO4-ZnS ) in AMD systems could reflect anaerobic, rather than aerobic pathways of oxidation. During the biological and abiotic oxidation of ZnS and ZnS Fe by Fe(III) aq all of the sulfate oxygen was derived from water, with measured ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of 8.2 ± 0.2‰ and 7.5 ± 0.1‰, respectively. Also, during the aerobic oxidation of ZnS Fe and S o by A . ferrooxidans , all of the sulfate oxygen was derived from water with similar measured ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of 8.1 ± 0.1‰ and 8.3 ± 0.3‰, respectively. During biological oxidation of ZnS by O 2 , an estimated 8% of sulfate–oxygen was derived from O 2 , which is enriched in 18 O relative to water, thus resulting in a larger apparent ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O value of 9.5‰. Based on the data presented we hypothesize that the similar ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of ∼8‰ from all of the aerobic and anaerobic experiments result from a common rate-limiting step that involves oxygen isotopic exchange between a sulfite ( SO 3 - "> SO3- ) intermediate and H 2 O. Our results indicate that the δ 18 O SO 4 "> δ18OSO4 values cannot be used to distinguish biological and abiotic, nor aerobic versus anaerobic, pathways of sphalerite oxidation. However, the ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of ∼8‰ measured here are distinctly higher than ε 18 O SO 4 - H 2 O "> ε18OSO4-H2O values of ∼4‰ previously reported for pyrite oxidation indicating the influence of sulfide mineralogy on measured δ 18 O SO 4 "> δ18OSO4 values.

Geochimica et Cosmochimica Acta↗

USGS2010

Laboratory chalcopyrite oxidation by Acidithiobacillus ferrooxidans: Oxygen and sulfur isotope fractionation

Laboratory experiments were conducted to simulate chalcopyrite oxidation under anaerobic and aerobic conditions in the absence or presence of the bacterium Acidithiobacillus ferrooxidans. Experiments were carried out with 3 different oxygen isotope values of water (?? 18 O H2O ) so that approach to equilibrium or steady-state isotope fractionation for different starting conditions could be evaluated. The contribution of dissolved O 2 and water-derived oxygen to dissolved sulfate formed by chalcopyrite oxidation was unambiguously resolved during the aerobic experiments. Aerobic oxidation of chalcopyrite showed 93 ?? 1% incorporation of water oxygen into the resulting sulfate during the biological experiments. Anaerobic experiments showed similar percentages of water oxygen incorporation into sulfate, but were more variable. The experiments also allowed determination of sulfate-water oxygen isotope fractionation, ?? 18 O SO4-H2O , of ~ 3.8??? for the anaerobic experiments. Aerobic oxidation produced apparent ?? SO4-H2O values (6.4???) higher than the anaerobic experiments, possibly due to additional incorporation of dissolved O 2 into sulfate. ?? 34 S SO4 values are ~ 4??? lower than the parent sulfide mineral during anaerobic oxidation of chalcopyrite, with no significant difference between abiotic and biological processes. For the aerobic experiments, a small depletion in ?? 34 S SO4 of ~- 1.5 ?? 0.2??? was observed for the biological experiments. Fewer solids precipitated during oxidation under aerobic conditions than under anaerobic conditions, which may account for the observed differences in sulfur isotope fractionation under these contrasting conditions. ?? 2009 Elsevier B.V.

Chemical Geology↗

USGS2008

Subsurface microbial diversity in deep-granitic-fracture water in Colorado

A microbial community analysis using 16S rRNA gene sequencing was performed on borehole water and a granite rock core from Henderson Mine, a >1,000-meter-deep molybdenum mine near Empire, CO. Chemical analysis of borehole water at two separate depths (1,044 m and 1,004 m below the mine entrance) suggests that a sharp chemical gradient exists, likely from the mixing of two distinct subsurface fluids, one metal rich and one relatively dilute; this has created unique niches for microorganisms. The microbial community analyzed from filtered, oxic borehole water indicated an abundance of sequences from iron-oxidizing bacteria ( Gallionella spp.) and was compared to the community from the same borehole after 2 weeks of being plugged with an expandable packer. Statistical analyses with UniFrac revealed a significant shift in community structure following the addition of the packer. Phospholipid fatty acid (PLFA) analysis suggested that Nitrosomonadales dominated the oxic borehole, while PLFAs indicative of anaerobic bacteria were most abundant in the samples from the plugged borehole. Microbial sequences were represented primarily by Firmicutes , Proteobacteria , and a lineage of sequences which did not group with any identified bacterial division; phylogenetic analyses confirmed the presence of a novel candidate division. This “Henderson candidate division” dominated the clone libraries from the dilute anoxic fluids. Sequences obtained from the granitic rock core (1,740 m below the surface) were represented by the divisions Proteobacteria (primarily the family Ralstoniaceae ) and Firmicutes . Sequences grouping within Ralstoniaceae were also found in the clone libraries from metal-rich fluids yet were absent in more dilute fluids. Lineage-specific comparisons, combined with phylogenetic statistical analyses, show that geochemical variance has an important effect on microbial community structure in deep, subsurface systems.

Applied and Environmental Microbiology↗

USGS2007

Oxygen and sulfur isotope systematics of sulfate produced by bacterial and abiotic oxidation of pyrite

To better understand reaction pathways of pyrite oxidation and biogeochemical controls on ??18O and ??34S values of the generated sulfate in acid mine drainage (AMD) and other natural environments, we conducted a series of pyrite oxidation experiments in the laboratory. Our biological and abiotic experiments were conducted under aerobic conditions by using O2 as an oxidizing agent and under anaerobic conditions by using dissolved Fe(III)aq as an oxidant with varying ??18OH2O values in the presence and absence of Acidithiobacillus ferrooxidans. In addition, aerobic biological experiments were designed as short- and long-term experiments where the final pH was controlled at ???2.7 and 2.2, respectively. Due to the slower kinetics of abiotic sulfide oxidation, the aerobic abiotic experiments were only conducted as long term with a final pH of ???2.7. The ??34SSO4 values from both the biological and abiotic anaerobic experiments indicated a small but significant sulfur isotope fractionation (???-0.7???) in contrast to no significant fractionation observed from any of the aerobic experiments. Relative percentages of the incorporation of water-derived oxygen and dissolved oxygen (O2) to sulfate were estimated, in addition to the oxygen isotope fractionation between sulfate and water, and dissolved oxygen. As expected, during the biological and abiotic anaerobic experiments all of the sulfate oxygen was derived from water. The percentage incorporation of water-derived oxygen into sulfate during the oxidation experiments by O2 varied with longer incubation and lower pH, but not due to the presence or absence of bacteria. These percentages were estimated as 85%, 92% and 87% from the short-term biological, long-term biological and abiotic control experiments, respectively. An oxygen isotope fractionation effect between sulfate and water (??18 OSO4 s(-) H2 O) of ???3.5??? was determined for the anaerobic (biological and abiotic) experiments. This measured ??18 OSO42 - s(-) H2 O value was then used to estimate the oxygen isotope fractionation effects (??18 OSO42 - s(-) O2) between sulfate and dissolved oxygen in the aerobic experiments which were -10.0???, -10.8???, and -9.8??? for the short-term biological, long-term biological and abiotic control experiments, respectively. Based on the similarity between ??18OSO4 values in the biological and abiotic experiments, it is suggested that ??18OSO4 values cannot be used to distinguish biological and abiotic mechanisms of pyrite oxidation. The results presented here suggest that Fe(III)aq is the primary oxidant for pyrite at pH < 3, even in the presence of dissolved oxygen, and that the main oxygen source of sulfate is water-oxygen under both aerobic and anaerobic conditions. ?? 2007 Elsevier Ltd. All rights reserved.

Geochimica et Cosmochimica Acta↗

USGS2006

Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared 56Fe/54Fe ratios of coexisting aqueous iron (Fe(II)aq, Fe(III)aq) and iron oxyhydroxide precipitates (Fe(III)ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO42- and Cl- salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, 56Fe/54Fe ratios of residual Fe(II)aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor ??Fe(III)aq-Fe(II)aq???1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (???1.0034) and that predicted for isotopic equilibrium between Fe(II)aq and Fe(III)aq (???1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in 56Fe/54Fe ratios between Fe(III)aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N2-atmosphere, and Fe(II)aq was in most cases and on average close to 2.9??? (??Fe(III)aq-Fe(II)aq ???1.0029), consistent with isotopic equilibrium between Fe(II)aq and Fe(III)aq. The ferric iron precipitation experiments revealed that 56Fe/54Fe ratios of Fe(III)aq were generally equal to or greater than those of Fe(III)ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record. ?? 2005 Elsevier Inc. All rights reserved.

Geochimica et Cosmochimica Acta↗

USGS2004

Effects of the fungicides mancozeb and chlorothalonil on fluxes of CO2, N2O, and CH4 in a fertilized Colorado grassland soil

[1] Management of agricultural soil plays an important role in present and future atmospheric concentrations of the greenhouse gases carbon dioxide (CO 2 ), nitrous oxide (N 2 O), and methane (CH 4 ). Pesticides are used as management tools in crop production, but little is known about their effects on soil‐atmosphere exchange of CO 2 , N 2 O, and CH 4 . Field studies described in this paper determined the effect of two commonly used fungicides, mancozeb and chlorothalonil, on trace gas exchange. Separate experimental plots, 1 m 2 , were established in nitrogen fertilized no‐tilled native grassland and tilled soils with and without fungicide application. Two studies were conducted. The first study was initiated in June 1999 and lasted for 1 year with monthly flux measurements from tilled and no‐till soils. The second study commenced in August 2001 with twelve weekly measurements from tilled soils only. From both studies mancozeb suppressed emissions of CO 2 and N 2 O in the tilled soil by an average of 28% and 47%, respectively. This suppression corresponded with efficacy periods of 14–29 and 56–77 days, respectively. From the no‐till soils mancozeb decreased CO 2 and N 2 O emissions by 33% and 80% for periods of 29 and 94 days, respectively. Mancozeb inhibited CH 4 consumption in the first study by 46% and 71% in the tilled and no‐till soil for periods of 8 and 29 days, respectively, but had no effect in the second study. From both studies chlorothalonil initially suppressed CO 2 and N 2 O emissions and enhanced CH 4 uptake in the tilled soil by an average of 37%, 40%, and 115%, respectively. These effects corresponded with efficacy periods of 14–29, 21–56, and 1–14 days, respectively. In the no‐till soil chlorothalonil inhibited CO 2 and N 2 O emissions and enhanced CH 4 uptake by 29%, 48%, and 86% for periods of 29, 56, and 56 days, respectively. Following the initial period of suppression, chlorothalonil subsequently enhanced N 2 O emissions in the tilled soil by an average of 51% and in the no‐till soil by 81% before returning to near background levels. The beginning of increased N 2 O emissions from the chlorothalonil‐amended plots corresponded with a maximum soil concentration of the chlorothalonil degradate, 4‐hydroxy‐2, 5, 6‐trichloroisophthalonitrile. The site specific global warming potential (GWP) resulting from the fluxes of CO 2 , N 2 O, and CH 4 from all soils was determined to decrease by an average 26% and 21% as a result of a single application of mancozeb or chlorothalonil, respectively. The decrease in CO 2 emissions in the fungicide‐amended plots potentially could result in the conservation of as much as 1200 and 2400 kg C ha −1 yr −1 organic carbon in the tilled and no‐till plots, respectively. Therefore it is feasible that application of certain fungicides to agricultural soil might lead to enhanced soil carbon sequestration and thus have additional positive effects on atmospheric CO 2 concentrations.

Journal of Geophysical Research D: Atmospheres↗

USGS2004

Effects of the herbicides prosulfuron and metolachlor on fluxes of CO2,N2O, and CH4 in a fertilized Colorado grassland soil

The effect that pesticides have on trace gas production and consumption in agricultural soils is often overlooked. Independent field and laboratory experiments were used to measure the effects that the commonly used herbicides prosulfuron and metolachlor have on trace gas fluxes (CO 2 , N 2 O, and CH 4 ) from fertilized soil of the Colorado shortgrass steppe. Separate sample plots (1 m 2 ) on tilled and no-till soil at the sites included the following treatments: 1) a control without fertilizer or herbicide, 2) a fertilized (NH 4 NO 3 equivalent to 244 kg ha −1 ) control without herbicide, 3) and fertilized plots amended with an herbicide (prosulfuron equivalent to 0.46 kg ha −1 57% by weight active ingredient or metolachlor equivalent to 5.7 L ha −1 , 82.4% by weight active ingredient). During an initial study of one year duration, measurement of gas exchange revealed that prosulfuron-amendment stimulated N 2 O emissions and CH 4 consumption by as much as 1600% and 1300% during a single measurement, respectively. During a second set of flux measurements beginning in August 2001, more frequent weekly measurements were made during a twelve week period. From this second study an increased N 2 O efflux and CH 4 uptake occurred after a 7-week lag period that persisted for about 5 weeks. These changes in gas flux amounted to an overall increase of 41% and 30% for N 2 O emission and CH 4 consumption, respectively. The co-occurrence of stimulated N 2 O and CH 4 fluxes suggests a similar cause that is related to prosulfuron degradation. Evidence suggested that prosulfuron degradation stimulated microbial activity responsible for trace gas flux. Ultimately, prosulfuron-amendment led to an ∼50% reduction in the global warming potential from N 2 O and CH 4 fluxes at this field site, which is equivalent to a reduction of the global warming potential of 0.18 mols CO 2 m −2 d −1 from these gases. Metolachlor application did not significantly affect the trace gas fluxes measured. These results demonstrate the potential impact that pesticides have on trace gas fluxes from agricultural soils, which could mean that the effects of other agricultural practices have been over or under estimated.

Colorado↗

USGS1999

Oxygen and iron isotope studies of magnetite produced by magnetotactic bacteria

A series of carefully controlled laboratory studies was carried out to investigate oxygen and iron isotope fractionation during the intracellular production of magnetite (Fe3O4) by two different species of magnetotactic bacteria at temperatures between 4??and 35??C under microaerobic and anaerobic conditions. No detectable fractionation of iron isotopes in the bacterial magnetites was observed. However, oxygen isotope measurements indicated a temperature-dependent fractionation for Fe3O4 and water that is consistent with that observed for Fe3O4 produced extracellularly by thermophilic Fe3+-reducing bacteria. These results contrast with established fractionation curves estimated from either high-temperature experiments or theoretical calculations. With the fractionation curve established in this report, oxygen-18 isotope values of bacterial Fe3O4 may be useful in paleoenvironmental studies for determining the oxygen-18 isotope values of formation waters and for inferring paleotemperatures.

Science↗