Thomas M. Johnson

Low Mid-Proterozoic atmospheric oxygen levels and the delayed rise of animals

Low oxygen limited the rise of animals Oxygen levels in Earths early atmosphere had an important influence on the evolution of complex life. Planavsky et al. analyzed the isotopic signature of chromium in sedimentary rocks from across the globe—a proxy for past oxygen levels. Oxygen levels in the mid-Proterozoic (1.6 billion to 900 million years ago) were very low: less than 0.1% of the modern atmosphere. These low levels were probably below the minimum oxygen requirements for the earliest animals, delaying their emergence and diversification. Science, this issue p. 635 Oxygen levels in Earth’s early atmosphere were often less than 1% of modern levels. The oxygenation of Earth’s surface fundamentally altered global biogeochemical cycles and ultimately paved the way for the rise of metazoans at the end of the Proterozoic. However, current estimates for atmospheric oxygen (O2) levels during the billion years leading up to this time vary widely. On the basis of chromium (Cr) isotope data from a suite of Proterozoic sediments from China, Australia, and North America, interpreted in the context of data from similar depositional environments from Phanerozoic time, we find evidence for inhibited oxidation of Cr at Earth’s surface in the mid-Proterozoic (1.8 to 0.8 billion years ago). These data suggest that atmospheric O2 levels were at most 0.1% of present atmospheric levels. Direct evidence for such low O2 concentrations in the Proterozoic helps explain the late emergence and diversification of metazoans.

Selenium isotope ratios as indicators of selenium sources and oxyanion reduction

Selenium stable isotope ratio measurements should serve as indicators of sources and biogeochemical transformations of Se. We report measurements of Se isotope fractionation during selenate reduction, selenite sorption, oxidation of reduced Se in soils, and Se volatilization by algae and soil samples. These results, combined with previous work with Se isotopes, indicate that reduction of soluble oxyanions is the dominant cause of Se isotope fractionation. Accordingly, Se isotope ratios should be useful as indicators of oxyanion reduction, which can transform mobile species to forms that are less mobile and less bioavailable. Additional investigations of Se isotope fractionation are needed to confirm this preliminary assessment. We have developed a new method for measurement of natural Se isotope ratio variation which requires less than 500 ng Se per analysis and yields ±0.2‰ precision on 80Se/76Se. A double isotope spike technique corrects for isotopic fractionation during sample preparation and mass spectrometry. The small minimum sample size is important, as Se concentrations are often below 1 ppm in solids and 1 μg/L in fluids. The Se purification process is rapid and compatible with various sample matrices, including acidic rock or sediment digests.

Interpretation of isotopic data in groundwater‐rock systems: Model development and application to Sr isotope data from Yucca Mountain

A model enabling extraction of hydrologic information from spatial and temporal patterns in measurements of isotope ratios in water-rock systems is presented. The model describes the evolution of isotope ratios in response to solute transport and water-rock interaction. In advective systems, a single dimensionless parameter (a Damkohler number, ND) dominates in determining the distance over which isotopic equilibrium between the water and rock is approached. Some isotope ratios act as conservative tracers (ND ≪ 1), while others reflect only interaction with the local host rock (ND ≫ 1). If ND is close to one (i.e., the distance for equilibration is close to the length scale of observation), isotope ratio measurements can be used to determine ND, which in turn may yield information concerning reaction rates, or spatial variations in water velocity. Zones of high velocity (e.g., as a result of greater fracture density), or less reactive zones, may be identified through observation of their lower ND values. The model is applied to paleohydrologic interpretations of Sr isotope data from calcite fracture fillings in drill cores from Yucca Mountain, Nevada (Marshall et al., 1992). The results agree with other studies suggesting “fast path” transport in the unsaturated zone. Also, we find that the data do not give a conclusive indication of paleowater table elevation because of the effects of water-rock interaction.

Paradox of groundwater age

Groundwater in aquifers is generally older than expected on the basis of flow velocity, and this observation has important implications for interpreting radiometric age determinations. Hydrologists commonly account for the aging of water as it flows along streamtubes, but not for the effects of mixing old water from aquitards (or confining layers) into aquifers, because the rate of mass exchange between aquifers and aquitards can in many cases be assumed to be small. We show, however, that the effect on age of such mixing does not depend on the mixing rate; this is the paradox of groundwater age. Surprisingly, the contribution of aquitards to the age of groundwater in aquifers depends only on the ratio of fluid volume in aquitards to aquifers. This result has broad importance for understanding the relationship between groundwater flow and the distribution of radiometric age.

Fractionation of selenium isotopes during bacterial respiratory reduction of selenium oxyanions

Reduction of selenium oxyanions by microorganisms is an important process in the biogeochemical cycling of selenium. Numerous bacteria can reduce Se oxyanions, which are used as electron acceptors during the oxidation of organic matter in anoxic environments. In this study, we used a double spike (82Se and 74Se) thermal ionization mass spectrometry technique to quantify the isotopic fractionation achieved by three different species of anaerobic bacteria capable of accomplishing growth by respiratory reduction of selenate [SeO42− or Se(VI)] or selenite [SeO32− or Se(IV)] to Se(IV) or elemental selenium [Se(0)] coupled with the oxidation of lactate. Isotopic discrimination in these closed system experiments was evaluated by Rayleigh fractionation equations and numerical models. Growing cultures of Bacillus selenitireducens, a haloalkaliphile capable of growth using Se(IV) as an electron acceptor, induced a 80Se/76Se fractionation of −8.0 ± 0.4‰ (instantaneous ϵ value) during reduction of Se(IV) to Se(0). With Bacillus arsenicoselenatis, a haloalkaliphile capable of growth using Se(VI) as an electron acceptor, fractionations of −5.0 ± 0.5‰ and −6.0 ± 1.0‰ were observed for reduction of Se(VI) to Se(IV) and reduction of Se(IV) to Se(0), respectively. In growing cultures of Sulfurospirillum barnesii, a freshwater species capable of growth using Se(VI), fractionation was small initially, but near the end of the log growth phase, it increased to −4.0 ± 1.0‰ and −8.4 ± 0.4‰ for reduction of Se(VI) to Se(IV) and reduction of Se(IV) to Se(0), respectively. Washed cell suspensions of S. barnesii induced fractionations of −1.1 ± 0.4‰ during Se(VI) reduction, and −9.1 ± 0.5% for Se(IV) reduction, with some evidence for smaller values (e.g., −1.7‰) in the earliest-formed Se(0) results. These results demonstrate that dissimilatory reduction of selenate or selenite induces significant isotopic fractionation, and suggest that significant Se isotope ratio variation will be found in nature.

Selenium isotope fractionation during reduction by Fe(II)-Fe(III) hydroxide-sulfate (green rust)

We have determined the extent of Se isotope fractionation induced by reduction of selenate by sulfate interlayered green rust (GRSO4), a Fe(II)-Fe(III) hydroxide-sulfate. This compound is known to reduce selenate to Se(0), and it is the only naturally relevant abiotic selenate reduction pathway documented to date. Se reduction reactions, when they occur in nature, greatly reduce Se mobility and bioavailability. Se stable isotope analysis shows promise as an indicator of Se reduction, and Se isotope fractionation by various Se reactions must be known in order to refine this tool. We measured the increase in the 80Se/76Se ratio of dissolved selenate as lighter isotopes were preferentially consumed during reduction by GRSO4. Six different experiments that used GRSO4 made by two methods, with varying solution compositions and pH, yielded identical isotopic fractionations. Regression of all the data yielded an instantaneous isotope fractionation of 7.36 ± 0.24‰. Selenate reduction by GRSO4 induces much greater isotopic fractionation than does bacterial selenate reduction. If selenate reduction by GRSO4 occurs in nature, it may be identifiable on the basis of its relatively large isotopic fractionation.

Variations in 238U/235U in uranium ore deposits: Isotopic signatures of the U reduction process?

The ability to measure 238U/235U to high precision presents an important new opportunity to study the fate and transport of uranium in the environment. The ratio of 238U/235U was determined by multicollector–inductively coupled plasma–mass spectrometer in six uranium ore samples representing two different classes of deposits. Significant offsets in 238U/235U are observed between uranium ores precipitated from groundwaters at low temperature versus hydrothermal deposits precipitated at high temperatures, reinforcing an observation made previously but lacking the needed precision. Specifically, tabular sandstone-type uranium deposits were found to be depleted in 235U, with a total offset between low-temperature deposits and higher temperature deposits of ≈1.0‰. We attribute this offset to reflect a temperature-dependent fractionation related to the nuclear field shift effect during chemical reduction of uranium in ambient temperature groundwaters.

Cr stable isotopes as indicators of Cr(VI) reduction in groundwater: a detailed time-series study of a point-source plume.

Chromium stable isotope ratios show promise as indicators of Cr(VI) reduction in groundwater, but no published study has yet demonstrated that expected relationships between (53)Cr/(52)Cr and Cr(VI) concentration, position, and time occur in an actual groundwater plume. We present an extensive data set from a point-source plume in Berkeley, CA; data extend over 5 years and 14 locations covering the entire plume. We interpret the data using a Rayleigh distillation model with an effective fractionation factor that incorporates an intrinsic fractionation factor determined from incubations of site sediments and accounts for reservoir effects in the restricted subsurface zones where Cr(VI) reduction is thought to occur. The groundwater (53)Cr/(52)Cr and Cr(VI) concentration data are consistent with a scenario where the system has reached a steady state: Cr(VI) reduction continues, the extent of reduction at any point is constant over time, reduction proceeds to completion at the downgradient edge of the plume, and the plume is no longer advancing. The overall consistency of the results with a reasonable model for the site supports the use of Cr isotope-based estimates of reduction, but we discuss current uncertainties and limitations of the approach as well.

Stable isotope fractionation of selenium by natural microbial consortia

The mobility and bioavailability of Se depend on its redox state, and reduction of Se oxyanions to less mobile, reduced species controls transport of this potentially toxic element in the environment. Stable isotope fractionation of Se is currently being developed as an indicator of Se immobilization through reduction. In this study, Se isotope fractionation resulting from reduction of Se(VI) and Se(IV) oxyanions by natural microbial consortia was measured in sediment slurry experiments under nearly natural conditions, with no substrate added. Experiments were conducted with a wide range of initial Se concentrations and with sediment and water from three locations with contrasting environmental settings. The products of Se(VI) and Se(IV) reduction were enriched in the lighter isotopes relative to the reactants. Shifts of −2.6‰ to −3.1‰ and −5.5‰ to −5.7‰, respectively, were observed in the 80Se/76Se ratio. These isotopic fractionations did not depend significantly on initial Se concentrations, which were varied from 22 μg/l to 8 mg/l, or on geochemical differences among the sediments. These results provide estimates of Se isotope fractionation in organic-rich wetland environments but may not be appropriate for substrate-poor aquifers and marine sediments.

Uranium 238U/235U isotope ratios as indicators of reduction: results from an in situ biostimulation experiment at Rifle, Colorado, U.S.A.

The attenuation of groundwater contamination via chemical reaction is traditionally evaluated by monitoring contaminant concentration through time. However, this method can be confounded by common transport processes (e.g., dilution, sorption). Isotopic techniques bypass the limits of concentration methods, and so may provide improved accuracy in determining the extent of reaction. We apply measurements of 238U/235U to a U bioremediation field experiment at the Rifle Integrated Field Research Challenge Site in Rifle, Colorado. An array of monitoring and injection wells was installed on a 100 m2 plot where U(VI) contamination was present in the groundwater. Acetate-amended groundwater was injected along an up-gradient gallery to encourage the growth of dissimilatory metal reducing bacteria (e.g., Geobacter species). During amendment, U concentration dropped by an order of magnitude in the experiment plot. We measured 238U/235U in samples from one monitoring well by MC-ICP-MS using a double isotope tracer method. A significant approximately 1.00 per thousand decrease in 238U/235U occurred in the groundwater as U(VI) concentration decreased. The relationship between 238U/235U and concentration corresponds approximately to a Rayleigh distillation curve with an effective fractionation factor (alpha) of 1.00046. We attribute the observed U isotope fractionation to a nuclear field shift effect during enzymatic reduction of U(VI)(aq) to U(IV)(s).