Monitoring Cr toxicity and remediation processes - combining a whole-cell bioreporter and Cr isotope techniques.

Bioremediation is a sustainable and cost-effective means of contaminant detoxification. Although Cr(VI) is toxic at high concentrations, various microbes can utilise it as an electron accepter in the bioremediation process, and reduce it to the less toxic form Cr(III). During remediation, it is important to monitor the level of toxicity and effectiveness of Cr(VI) reduction in order to optimize the conditions. This study employed a whole-cell bioreporter Acinetobacter baylyi ADPWH-recA to access the degree of toxicity of different species of Cr over a range of initial concentrations. It also investigated whether Cr isotope fractionation factors were impacted by different levels of Cr toxicity (related to its concentration) and Cr(VI) reduction rates by Cr resistant bacteria Pseudomonas fluorescens LB 300. The results show that, of both Cr2O72- and CrO42-, the whole-cell bioreporter was efficient in indicating the level of genotoxicity of Cr(VI) at low concentrations and cytotoxicity at high concentrations via variations of bioluminescence. High concentrations (> 100 mg/L) of Cr(III) could also strongly induce the luminescence in the bioreporter, indicating DNA damage at such abundance. Pseudomonas fluorescens LB 300 was found to be effective in reducing Cr(VI) even when the concentration was high (40 mg/L); however, complete Cr(VI) reduction was only observed at low concentrations (< 5 mg/L), since the toxicity of high concentrations of Cr(VI) impacted the effectiveness of reduction by the bacteria. During reduction, the C53r/C52r ratio of remaining Cr(VI) increased from its initial value, and the calculated fractionation factor by bacterial Cr(VI) reduction (ε) was -3.1±0.3‰. The fractionation factor was independent of the initial Cr(VI) concentration. Therefore, a single Cr isotope fractionation factor can be effectively applied in indicating the extent of bioremediation processing of Cr(VI) over a wide range of concentrations. This significantly simplified monitoring of Cr(VI) depletion in bioremediation, since variations of ε normally indicate a change in the reduction mechanism and therefore would complicate the elucidation of processes driving the remediation.

Using stable isotope fractionation factors to identify Cr(VI) reduction pathways: Metal-mineral-microbe interactions.

Microbes interact with metals and minerals in the environment altering their physical and chemical states, whilst in turn metals and minerals impact on microbial growth, activity and survival. The interactions between bacteria and dissolved chromium in the presence of iron minerals, and their impact on Cr isotope variations, were investigated. Cr(VI) reduction experiments were conducted with two bacteria, Pseudomonas fluorescens LB 300 and Shewanella oneidensis MR-1, in the presence of two iron oxide minerals, goethite and hematite. Both minerals were found to inhibit the rates of Cr(VI) reduction by Pseudomonas, but accelerated those of Shewanella. The Cr isotopic fractionation factors generated by Shewanella were independent of the presence of the minerals (ε = -2.3‰). For Pseudomonas, the ε value was the same in both the presence and absence of goethite (-3.3‰); although, it was much higher (ε = -4.3‰) in the presence of hematite. The presence of aqueous Fe(III) in solution had no detectable impact on either bacterial Cr reduction rates nor isotopic fractionation factors. The presence of aqueous Fe(II) induced rapid abiotic reduction of Cr(VI). The different effects that the presence of Fe minerals had on the Cr fractionation factors and reduction rates of the different bacterial species may be attributed to the way each bacteria attached to the minerals and their different reduction pathways. SEM images confirmed that Pseudomonas cells were much more tightly packed on the mineral surfaces than were Shewanella. The images also confirmed that Shewanella oneidensis MR-1 produced nanowires. The results suggest that the dominant Cr(VI) reduction pathway for Pseudomonas fluorescens LB 300 may have been through membrane-bound enzymes, whilst for Shewanella oneidensis MR-1 it was probably via extracellular electron transfer. Since different minerals impact differentially on bacterial Cr(VI) reduction and isotope fractionation, variations of mineralogies and the associated changes of bacterial communities should be taken into consideration when using Cr isotopes to quantify Cr redox behaviour in the environment.

Uranium isotope evidence for two episodes of deoxygenation during Oceanic Anoxic Event 2.

Oceanic Anoxic Event 2 (OAE 2), occurring ∼94 million years ago, was one of the most extreme carbon cycle and climatic perturbations of the Phanerozoic Eon. It was typified by a rapid rise in atmospheric CO2, global warming, and marine anoxia, leading to the widespread devastation of marine ecosystems. However, the precise timing and extent to which oceanic anoxic conditions expanded during OAE 2 remains unresolved. We present a record of global ocean redox changes during OAE 2 using a combined geochemical and carbon cycle modeling approach. We utilize a continuous, high-resolution record of uranium isotopes in pelagic and platform carbonate sediments to quantify the global extent of seafloor anoxia during OAE 2. This dataset is then compared with a dynamic model of the coupled global carbon, phosphorus, and uranium cycles to test hypotheses for OAE 2 initiation. This unique approach highlights an intra-OAE complexity that has previously been underconstrained, characterized by two expansions of anoxia separated by an episode of globally significant reoxygenation coincident with the "Plenus Cold Event." Each anoxic expansion event was likely driven by rapid atmospheric CO2 injections from multiphase Large Igneous Province activity.

Advanced Residuals Analysis for Determining the Number of PARAFAC Components in Dissolved Organic Matter.

Parallel factor analysis (PARAFAC) has facilitated an explosion in research connecting the fluorescence properties of dissolved organic matter (DOM) to its functions and biogeochemical cycling in natural and engineered systems. However, the validation of robust PARAFAC models using split-half analysis requires an oft unrealistically large number (hundreds to thousands) of excitation-emission matrices (EEMs), and models with too few components may not adequately describe differences between DOM. This study used self-organizing maps (SOM) and comparing changes in residuals with the effects of adding components to estimate the number of PARAFAC components in DOM from two data sets: MS (110 EEMs from nine leaf leachates and headwaters) and LR (64 EEMs from the Lena River). Clustering by SOM demonstrated that peaks clearly persisted in model residuals after validation by split-half analysis. Plotting the changes to residuals was an effective method for visualizing the removal of fluorophore-like fluorescence caused by increasing the number of PARAFAC components. Extracting additional PARAFAC components via residuals analysis increased the proportion of correctly identified size-fractionated leaf leachates from 56.0 ± 0.8 to 75.2 ± 0.9%, and from 51.7 ± 1.4 to 92.9 ± 0.0% for whole leachates. Model overfitting was assessed by considering the correlations between components, and their distributions amongst samples. Advanced residuals analysis improved the ability of PARAFAC to resolve the variation in DOM fluorescence, and presents an enhanced validation approach for assessing the number of components that can be used to supplement the potentially misleading results of split-half analysis.

Coastal ocean and shelf-sea biogeochemical cycling of trace elements and isotopes: lessons learned from GEOTRACES.

Continental shelves and shelf seas play a central role in the global carbon cycle. However, their importance with respect to trace element and isotope (TEI) inputs to ocean basins is less well understood. Here, we present major findings on shelf TEI biogeochemistry from the GEOTRACES programme as well as a proof of concept for a new method to estimate shelf TEI fluxes. The case studies focus on advances in our understanding of TEI cycling in the Arctic, transformations within a major river estuary (Amazon), shelf sediment micronutrient fluxes and basin-scale estimates of submarine groundwater discharge. The proposed shelf flux tracer is 228-radium (T1/2 = 5.75 yr), which is continuously supplied to the shelf from coastal aquifers, sediment porewater exchange and rivers. Model-derived shelf 228Ra fluxes are combined with TEI/ 228Ra ratios to quantify ocean TEI fluxes from the western North Atlantic margin. The results from this new approach agree well with previous estimates for shelf Co, Fe, Mn and Zn inputs and exceed published estimates of atmospheric deposition by factors of approximately 3-23. Lastly, recommendations are made for additional GEOTRACES process studies and coastal margin-focused section cruises that will help refine the model and provide better insight on the mechanisms driving shelf-derived TEI fluxes to the ocean.This article is part of the themed issue 'Biological and climatic impacts of ocean trace element chemistry'.

Determination of Nd isotopes in water: a chemical separation technique for extracting Nd from seawater using a chelating resin.

A new preconcentration technique for the determination of the concentration and isotopic composition of neodymium in aqueous samples is presented. The method uses a resin, Nobias PA1 from Hitachi High-Technologies, which has a hydrophilic methacrylate polymer backbone where the functional groups ethylenediaminetriacetic and iminodiacetic acids are immobilized. The function of the resin has been tested by preconcentrating 110-350 pmol of Nd from test solutions as well as from natural brackish water and seawater samples with different salinities and Nd concentrations. Samples were loaded onto the resin after the pH was adjusted, and the Nd fraction was eluted using 3 M HNO(3). The method shows yields of about 90% or higher at pH 6 when the samples were buffered using ammonium acetate. Without the addition of buffer the yield decreased to below 80%. The isotopic composition of Nd in samples preconcentrated using Nobias PA1 agree within error with published data or data obtained by other methods. The total blank, including contributions from preconcentration, separation, and mass spectrometry, is estimated to be 0.2-0.4 pmol (30-60 pg) of Nd. The described preconcentration method, which can be used in the field, is easy, fast (about 8 h for a 3.6 kg sample), and reliable for preconcentration of Nd from a seawater matrix.

Partitioning experiments in the laser-heated diamond anvil cell: volatile content in the Earth's core.

The present state of the Earth evolved from energetic events that were determined early in the history of the Solar System. A key process in reconciling this state and the observable mantle composition with models of the original formation relies on understanding the planetary processing that has taken place over the past 4.5Ga. Planetary size plays a key role and ultimately determines the pressure and temperature conditions at which the materials of the early solar nebular segregated. We summarize recent developments with the laser-heated diamond anvil cell that have made possible extension of the conventional pressure limit for partitioning experiments as well as the study of volatile trace elements. In particular, we discuss liquid-liquid, metal-silicate (M-Sil) partitioning results for several elements in a synthetic chondritic mixture, spanning a wide range of atomic number-helium to iodine. We examine the role of the core as a possible host of both siderophile and trace elements and the implications that early segregation processes at deep magma ocean conditions have for current mantle signatures, both compositional and isotopic. The results provide some of the first experimental evidence that the core is the obvious replacement for the long-sought, deep mantle reservoir. If so, they also indicate the need to understand the detailed nature and scale of core-mantle exchange processes, from atomic to macroscopic, throughout the age of the Earth to the present day.

The contemporary degassing rate of 40Ar from the solid Earth.

Knowledge of the outgassing history of radiogenic (40)Ar, derived over geologic time from the radioactive decay of (40)K, contributes to our understanding of the geodynamic history of the planet and the origin of volatiles on Earth's surface. The (40)Ar inventory of the atmosphere equals total (40)Ar outgassing during Earth history. Here, we report the current rate of (40)Ar outgassing, accessed by measuring the Ar isotope composition of trapped gases in samples of the Vostok and Dome C deep ice cores dating back to almost 800 ka. The modern outgassing rate (1.1 +/- 0.1 x 10(8) mol/yr) is in the range of values expected by summing outgassing from the continental crust and the upper mantle, as estimated from simple calculations and models. The measured outgassing rate is also of interest because it allows dating of air trapped in ancient ice core samples of unknown age, although uncertainties are large (+/-180 kyr for a single sample or +/-11% of the calculated age, whichever is greater).

Numerical models, geochemistry and the zero-paradox noble-gas mantle.

Numerical models of whole-mantle convection demonstrate that degassing of the mantle is an inefficient process, resulting in ca. 50% of the (40)Ar being degassed from the mantle system. In this sense the numerical simulations are consistent with the (40)Ar mass balance between the atmosphere and mantle reservoir. These models, however, are unable to preserve the large-scale heterogeneity predicted by models invoking geochemical layering of the mantle system. We show that the three most important noble-gas constraints on the geochemically layered mantle are entirely dependent on the (3)He concentration of the convecting mantle derived from the (3)He flux into the oceans and the average ocean-crust generation rate. A factor of 3.5 increase in the convecting-mantle noble-gas concentration removes all requirements for: a (3)He flux into the upper mantle from a deeper high (3)He source; a boundary in the mantle capable of separating heat from helium; and a substantial deep-mantle reservoir to contain a hidden (40)Ar rich reservoir. We call this model concentration for the convecting mantle the 'zero-paradox' concentration. The time-integrated flux of (3)He into the oceans is a robust observation, but only representative of the ocean-floor activity over the last 1000 years. In contrast, ocean-floor generation occurs over tens of millions of years. We argue that combining these two observations to obtain the (3)He concentration of the mantle beneath mid-ocean ridges is unsound. Other indicators of mantle (3)He concentration suggest that the real value may be at least a factor of two higher. As the zero-paradox concentration is approached, the noble-gas requirement for mantle layering is removed. We further consider the role that recycled material plays in ocean-island-basalt generation and show that a source with high (3)He and (3)He/(4)He must exist within the mantle. Nevertheless, only a small amount of this material is required to generate both the observed ocean-island (3)He/(4)He ratios and the concentrations inferred from basalt samples for this mantle source.