Deep weathering in the semi-arid Coastal Cordillera, Chile.

The weathering front is the boundary beneath Earth's surface where pristine rock is converted into weathered rock. It is the base of the "critical zone", in which the lithosphere, biosphere, and atmosphere interact. Typically, this front is located no more than 20 m deep in granitoid rock in humid climate zones. Its depth and the degree of rock weathering are commonly linked to oxygen transport and fluid flow. By drilling into fractured igneous rock in the semi-arid climate zone of the Coastal Cordillera in Chile we found multiple weathering fronts of which the deepest is 76 m beneath the surface. Rock is weathered to varying degrees, contains core stones, and strongly altered zones featuring intensive iron oxidation and high porosity. Geophysical borehole measurements and chemical weathering indicators reveal more intense weathering where fracturing is extensive, and porosity is higher than in bedrock. Only the top 10 m feature a continuous weathering gradient towards the surface. We suggest that tectonic preconditioning by fracturing provided transport pathways for oxygen to greater depths, inducing porosity by oxidation. Porosity was preserved throughout the weathering process, as secondary minerals were barely formed due to the low fluid flow.

Quantifying beryllium concentrations in plant shoots from forest ecosystems using cation-exchange chromatography and quadrupole ICP-MS.

Beryllium (Be) is known to be one of the most toxic elements but at the same time exerts a stimulating effect on plant growth. Despite this contradiction, little is known about the Be metabolism in living organisms, partially because of the low amounts present and because the analysis of Be in plants by ICP-MS remains challenging. The challenges arise from the complex organic matrix, the low abundance of Be relative to the other plant essential elements, and the matrix effects resulting thereof in the plasma. To address these challenges, we developed and evaluated a new method for Be concentration analysis in plant material. Key is the quantitative separation of Be from the other matrix elements by cation-exchange chromatography. The new method was verified by processing seven reference materials representing different plant matrices yielding a long-term reproducibility of 16% (RSD). Applying the method, Be concentrations in tree, shrub, bush, and grass samples grown in non-polluted ecosystems from four temperate forests and a tropical rainforest were measured. The Be concentrations in different plant organs range from 0.01 to 63 ng/g that suggest a natural baseline for Be concentrations of 52 ng/g (95 percentile of non-woody tissue) that may serve as bioindicator for Be pollution in the environment. Comparison of Be concentrations in plants with the soil's biologically available fraction revealed that Be is discriminated from uptake into shoots and thus can be considered as non-essential.

Neogene cooling driven by land surface reactivity rather than increased weathering fluxes.

The long-term cooling, decline in the partial pressure of carbon dioxide, and the establishment of permanent polar ice sheets during the Neogene period1,2 have frequently been attributed to increased uplift and erosion of mountains and consequent increases in silicate weathering, which removes atmospheric carbon dioxide3,4. However, geological records of erosion rates are potentially subject to averaging biases5,6, and the magnitude of the increase in weathering fluxes-and even its existence-remain debated7-9. Moreover, an increase in weathering scaled to the proposed erosional increase would have removed nearly all carbon from the atmosphere10, which has led to suggestions of compensatory carbon fluxes11-13 in order to preserve mass balance in the carbon cycle. Alternatively, an increase in land surface reactivity-resulting from greater fresh-mineral surface area or an increase in the supply of reactive minerals-rather than an increase in the weathering flux, has been proposed to reconcile these disparate views8,9. Here we use a parsimonious carbon cycle model that tracks two weathering-sensitive isotopic tracers (stable 7Li/6Li and cosmogenic 10Be/9Be) to show that an increase in land surface reactivity is necessary to simultaneously decrease atmospheric carbon dioxide, increase seawater 7Li/6Li and retain constant seawater 10Be/9Be over the past 16 million years. We find that the global silicate weathering flux remained constant, even as the global silicate weathering intensity-the fraction of the total denudation flux that is derived from silicate weathering-decreased, sustained by an increase in erosion. Long-term cooling during the Neogene thus reflects a change in the partitioning of denudation into weathering and erosion. Variable partitioning of denudation and consequent changes in silicate weathering intensity reconcile marine isotope and erosion records with the need to maintain mass balance in the carbon cycle and without requiring increases in the silicate weathering flux.

Magnesium Stable Isotope Fractionation on a Cellular Level Explored by Cyanobacteria and Black Fungi with Implications for Higher Plants.

In a controlled growth experiment we found that the cyanobacterium Nostoc punctiforme has a bulk cell 26Mg/24Mg ratio (expressed as δ26Mg) that is -0.27‰ lower than the growth solution at a pH of ca. 5.9. This contrasts with a recently published δ26Mg value that was 0.65‰ higher than growth solution for the black fungus Knufia petricola at similar laboratory conditions, interpreted to reflect loss of 24Mg during cell growth. By a mass balance model constrained by δ26Mg in chlorophyll extract we inferred the δ26 Mg value of the main Mg compartments in a cyanobacteria cell: free cytosolic Mg (-2.64‰), chlorophyll (1.85‰), and the nonchlorophyll-bonded Mg compartments like ATP and ribosomes (-0.64‰). The lower δ26Mg found in Nostoc punctiforme would thus result from the absence of significant Mg efflux during cell growth in combination with either (a) discrimination against 26Mg during uptake by desolvation of Mg or transport across protein channels or (b) discrimination against 24Mg in the membrane transporter during efflux. The model predicts the preferential incorporation of 26Mg in cells and plant organs low in Mg and the absence of isotope fractionation in those high in Mg, corroborated by a compilation of Mg isotope ratios from fungi, bacteria, and higher plants.

Late Neoproterozoic seawater oxygenation by siliceous sponges.

The Cambrian explosion, the rapid appearance of most animal phyla in the geological record, occurred concurrently with bottom seawater oxygenation. Whether this oxygenation event was triggered through enhanced nutrient supply and organic carbon burial forced by increased continental weathering, or by species engaging in ecosystem engineering, remains a fundamental yet unresolved question. Here we provide evidence for several simultaneous developments that took place over the Ediacaran-Cambrian transition: expansion of siliceous sponges, decrease of the dissolved organic carbon pool, enhanced organic carbon burial, increased phosphorus removal and seawater oxygenation. This evidence is based on silicon and carbon stable isotopes, Ge/Si ratios, REE-geochemistry and redox-sensitive elements in a chert-shale succession from the Yangtze Platform, China. According to this reconstruction, sponges have initiated seawater oxygenation by redistributing organic carbon oxidation through filtering suspended organic matter from seawater. The resulting increase in dissolved oxygen levels potentially triggered the diversification of eumetazoans.The Ediacaran-Cambrian oxygenation of seawater is thought to have been caused by lifeforms engaging in ecosystem engineering. Here, the authors show that siliceous sponges increased seawater dissolved oxygen concentrations by redistributing organic carbon oxidation through filtering suspended organic matter.

Mg Isotope Fractionation during Uptake by a Rock-Inhabiting, Model Microcolonial Fungus Knufia petricola at Acidic and Neutral pH.

The model rock-inhabiting microcolonial fungus Knufia petricola fractionates stable Mg isotopes in a time- and pH-dependent manner. During growth, the increase of 26Mg/24Mg in the fungal cells relative to the growth media amounted to 0.65 ± 0.14‰ at pH 6 and 1.11 ± 0.35‰ at pH 3. We suggest a constant equilibrium fractionation factor during incorporation of Mg into ribosomes and ATP as a cause of enrichment of 26Mg in the cells. We suggest too that the proton gradient across the cell wall and cytoplasmic membrane controls Mg2+ transport into the fungal cell. As the strength of this gradient is a function of extracellular solution pH, the pH-dependence on Mg isotope fractionation is thus due to differences in fungal cell mass fluxes. Through a mass balance model we show that Mg uptake into the fungal cell is not associated with a unique Mg isotope fractionation factor. This Mg isotope fractionation dependence on pH might also be observed in any organism with cells that follow similar Mg uptake and metabolic pathways and serves to reveal Mg cycling in ecosystems.

Development of routines for simultaneous in situ chemical composition and stable Si isotope ratio analysis by femtosecond laser ablation inductively coupled plasma mass spectrometry.

Stable metal (e.g. Li, Mg, Ca, Fe, Cu, Zn, and Mo) and metalloid (B, Si, Ge) isotope ratio systems have emerged as geochemical tracers to fingerprint distinct physicochemical reactions. These systems are relevant to many Earth Science questions. The benefit of in situ microscale analysis using laser ablation (LA) over bulk sample analysis is to use the spatial context of different phases in the solid sample to disclose the processes that govern their chemical and isotopic compositions. However, there is a lack of in situ analytical routines to obtain a samples' stable isotope ratio together with its chemical composition. Here, we evaluate two novel analytical routines for the simultaneous determination of the chemical and Si stable isotope composition (δ(30)Si) on the micrometre scale in geological samples. In both routines, multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS) is combined with femtosecond-LA, where stable isotope ratios are corrected for mass bias using standard-sample-bracketing with matrix-independent calibration. The first method is based on laser ablation split stream (LASS), where the laser aerosol is split and introduced simultaneously into both the MC-ICP-MS and a quadrupole ICP-MS. The second method is based on optical emission spectroscopy using direct observation of the MC-ICP-MS plasma (LA-MC-ICP-MS|OES). Both methods are evaluated using international geological reference materials. Accurate and precise Si isotope ratios were obtained with an uncertainty typically better than 0.23‰, 2SD, δ(30)Si. With both methods major element concentrations (e.g., Na, Al, Si, Mg, Ca) can be simultaneously determined. However, LASS-ICP-MS is superior over LA-MC-ICP-MS|OES, which is limited by its lower sensitivity. Moreover, LASS-ICP-MS offers trace element analysis down to the µg g(-1)-range for more than 28 elements due to lower limits of detection, and with typical uncertainties better than 15%. For in situ simultaneous stable isotope measurement and chemical composition analysis LASS-ICP-MS in combination with MC-ICP-MS is the method of choice.

An iron stable isotope comparison between human erythrocytes and plasma.

We present precise iron stable isotope ratios measured by multicollector-ICP mass spectrometry (MC-ICP-MS) of human red blood cells (erythrocytes) and blood plasma from 12 healthy male adults taken during a clinical study. The accurate determination of stable isotope ratios in plasma first required substantial method development work, as minor iron amounts in plasma had to be separated from a large organic matrix prior to mass-spectrometric analysis to avoid spectroscopic interferences and shifts in the mass spectrometer's mass-bias. The (56)Fe/(54)Fe ratio in erythrocytes, expressed as permil difference from the "IRMM-014" iron reference standard (δ(56/54)Fe), ranges from -3.1‰ to -2.2‰, a range typical for male Caucasian adults. The individual subject erythrocyte iron isotope composition can be regarded as uniform over the 21 days investigated, as variations (±0.059 to ±0.15‰) are mostly within the analytical precision of reference materials. In plasma, δ(56/54)Fe values measured in two different laboratories range from -3.0‰ to -2.0‰, and are on average 0.24‰ higher than those in erythrocytes. However, this difference is barely resolvable within one standard deviation of the differences (0.22‰). Taking into account the possible contamination due to hemolysis (iron concentrations are only 0.4 to 2 ppm in plasma compared to approx. 480 ppm in erythrocytes), we model the pure plasma δ(56/54)Fe to be on average 0.4‰ higher than that in erythrocytes. Hence, the plasma iron isotope signature lies between that of the liver and that of erythrocytes. This difference can be explained by redox processes involved during cycling of iron between transferrin and ferritin.

Iron uptake and ferrokinetics in healthy male subjects of an iron-based oral phosphate binder (SBR759) labeled with the stable isotope (58)Fe.

SBR759 is a novel polynuclear iron(III) oxide-hydroxide starch·sucrose·carbonate complex being developed for oral use in chronic kidney disease (CKD) patients with hyperphosphatemia on hemodialysis. SBR759 binds inorganic phosphate released by food uptake and digestion in the gastro-intestinal tract increasing the fecal excretion of phosphate with concomitant reduction of serum phosphate concentrations. Considering the high content of ∼20% w/w covalently bound iron in SBR759 and expected chronic administration to patients, absorption of small amounts of iron released from the drug substance could result in potential iron overload and toxicity. In a mechanistic iron uptake study, 12 healthy male subjects (receiving comparable low phosphorus-containing meal typical for CKD patients: ≤1000 mg phosphate per day) were treated with 12 g (divided in 3 × 4 g) of stable (58)Fe isotope-labeled SBR759. The ferrokinetics of [(58)Fe]SBR759-related total iron was followed in blood (over 3 weeks) and in plasma (over 26 hours) by analyzing with high precision the isotope ratios of the natural iron isotopes (58)Fe, (57)Fe, (56)Fe and (54)Fe by multi-collector inductively coupled mass spectrometry (MC-ICP-MS). Three weeks following dosing, the subjects cumulatively absorbed on average 7.8 ± 3.2 mg (3.8-13.9 mg) iron corresponding to 0.30 ± 0.12% (0.15-0.54%) SBR759-related iron which amounts to approx. 5-fold the basal daily iron absorption of 1-2 mg in humans. SBR759 was well-tolerated and there was no serious adverse event and no clinically significant changes in the iron indices hemoglobin, hematocrit, ferritin concentration and transferrin saturation.

The iron stable isotope fingerprint of the human diet.

The stable isotopes of iron disclose the metabolic pathways of iron within the human food chain. We have measured with precise multicollector ICP-MS the iron concentrations and stable isotope composition of 60 food products that are representative of the average German diet. We find that vegetables fall within the range typical of strategy I plants (-0.1 to -1.4‰ in δ(56)Fe), crop products and processed crop foods into the range typical of strategy II plants (-0.6 to +0.4‰), and animal products into the (54)Fe-enriched range known for animal tissue and blood (-1.1 to -2.7‰). Weighting these isotope compositions by the average iron dietary sources, we find a representative composition of European vegetarian diet of -0.45‰, whereas that of omnivores is -0.82‰. For human blood, known to be enriched in light iron isotopes, we find fractionation factors for iron absorption of -2.0 and -2.3‰ for vegetarians (female and male, respectively) and -1.3 and -1.5‰ for omnivores (female and male, respectively). Knowing these fractionation factors is a prerequisite for using stable iron isotope ratios in blood as monitors of intestinal iron uptake regulation.

Long-term stability of global erosion rates and weathering during late-Cenozoic cooling.

Over geologic timescales, CO(2) is emitted from the Earth's interior and is removed from the atmosphere by silicate rock weathering and organic carbon burial. This balance is thought to have stabilized greenhouse conditions within a range that ensured habitable conditions. Changes in this balance have been attributed to changes in topographic relief, where varying rates of continental rock weathering and erosion are superimposed on fluctuations in organic carbon burial. Geological strata provide an indirect yet imperfectly preserved record of this change through changing rates of sedimentation. Widespread observations of a recent (0-5-Myr) fourfold increase in global sedimentation rates require a global mechanism to explain them. Accelerated uplift and global cooling have been given as possible causes, but because of the links between rates of erosion and the correlated rate of weathering, an increase in the drawdown of CO(2) that is predicted to follow may be the cause of global climate change instead. However, globally, rates of uplift cannot increase everywhere in the way that apparent sedimentation rates do. Moreover, proxy records of past atmospheric CO(2) provide no evidence for this large reduction in recent CO(2) concentrations. Here we question whether this increase in global weathering and erosion actually occurred and whether the apparent increase in the sedimentation rate is due to observational biases in the sedimentary record. As evidence, we recast the ocean dissolved (10)Be/(9)Be isotope system as a weathering proxy spanning the past approximately 12 Myr (ref. 14). This proxy indicates stable weathering fluxes during the late-Cenozoic era. The sum of these observations shows neither clear evidence for increased erosion nor clear evidence for a pulse in weathered material to the ocean. We conclude that processes different from an increase in denudation caused Cenozoic global cooling, and that global cooling had no profound effect on spatially and temporally averaged weathering rates.

Subsurface filamentous fabrics: an evaluation of origins based on morphological and geochemical criteria, with implications for exopaleontology.

The fossil record of the subsurface biosphere is sparse. Results obtained on subsurface filamentous fabrics (SFF) from >225 paleosubsurface sites in volcanics, oxidized ores, and paleokarst of subrecent to Proterozoic age are presented. SFF are mineral encrustations on filamentous or fibrous substrates that formed in subsurface environments. SFF occur in association with low-temperature aqueous mineral assemblages and consist of tubular, micron-thick (median 1.6 micron) filaments in high spatial density, which occur as irregular masses, matted fabrics, and vertically draped features that resemble stalactites. Micron-sized filamentous centers rule out a stalactitic origin. Morphometric analysis of SFF filamentous forms demonstrates that their shape more closely resembles microbial filaments than fibrous minerals. Abiogenic filament-like forms are considered unlikely precursors of most SFF, because abiogenic forms differ in the distribution of widths and have a lower degree of curvature and a lower number of direction changes. Elemental analyses of SFF show depletion in immobile elements (e.g., Al, Th) and a systematic enrichment in As and Sb, which demonstrates a relation to environments with high flows of water. Sulfur isotopic analyses are consistent with a biological origin of a SFF sample from a Mississippi Valley-Type deposit, which is consistent with data in the literature. Fe isotopes in SFF and active analogue systems, however, allow no discrimination between biogenic and abiogenic origins. The origin of most SFF is explained as permineralized remains of microbial filaments that possibly record rapid growth during phases of high water flow that released chemical energy. It is possible that some SFF formed due to encrustation of mineral fibers. SFF share similarities with Microcodium from soil environments. SFF are a logical target in the search for past life on Mars. The macroscopic nature of many SFF allows for their relatively easy in situ recognition and targeting for more detailed microstructural and geochemical analysis.

Fractionation of stable iron isotopes in higher plants.

Although the fractionation of stable iron isotopes by biological processes in the environment is currently a matter of intense debate, the isotope fractionation associated with the growth of higher plants has, to date, not been characterized. We show that iron isotope fractionation induced by higher plants is substantial and also generates systematic plant-specific patterns. We suggest a hypothesis in which these patterns mirror the two different strategies that plants have developed to incorporate iron from the soil: reduction of Fe(III) in soils by strategy I plants results in the uptake of iron, which is depleted in 56Fe by up to 1.6 per mil relative to 54Fe when compared to the available Fe in soils; complexation with siderophores by strategy II plants results in the uptake of iron that is 0.2 per mil heavier than that in soils. Furthermore, younger parts of strategy I plants get increasingly depleted in heavy isotopes as the plant grows, while strategy II plants incorporate nearly the same isotope composition throughout. This points to entirely different translocation mechanisms between strategy I and II plants. Such presumably redox-related differences in translocation have been under debate up to now. We conclude that plant metabolism represents an important cause of isotopic variation in the biogeochemical cycling of Fe. Therefore, heavy stable metal isotope systems now start to be viable indicators of geosphere-biosphere metal transfer processes.

Hereditary hemochromatosis is reflected in the iron isotope composition of blood.

It has recently been shown that the iron isotopic composition of blood differs between individuals and sexes, which is supposed to reflect individual differences in iron metabolism. We hypothesized that patients suffering from hereditary hemochromatosis would demonstrate alterations in the iron isotopic composition of blood due to persistent up-regulation of intestinal iron absorption. Blood from 30 patients with homozygous C282Y hemochromatosis was analyzed for iron isotopic composition by a newly developed technique using multicollector inductively coupled plasma mass spectrometry (MC-ICP-MS). Blood of patients with hemochromatosis is characterized by a higher 56Fe/54Fe isotope ratio than blood of healthy individuals, which are either members of an age-matched control group (n = 10; P < .001) or young adults (n = 36; P < .001). In patients with hereditary hemochromatosis, the 56Fe/54Fe isotope ratio of blood significantly correlates with total-body iron accumulation, severity of clinical disease, and the need for regular phlebotomies to prevent iron reaccumulation. We conclude that blood of patients with hereditary hemochromatosis contains more of the heavier iron isotopes than blood of healthy individuals. The primary determinant of the iron isotopic composition of blood appears to be isotope-sensitive iron absorption in the intestine and the efficiency of this process.

Natural iron isotope variations in human blood.

Isotopic analysis of human blood and liver and muscle tissue indicates that each individual bears a long-term iron (Fe) isotope signature in the blood. Blood and tissue differ slightly in isotopic composition and are depleted by up to 2.6 per mil in 56Fe relative to 54Fe when compared to dietary Fe. The 56Fe/54Fe isotope ratio in the blood of males is, on average, lower by 0.3 per mil than that of females. These results suggest that Fe isotope effects in the blood reflect differences in intestinal Fe absorption between individuals and genotypes.