Study of diatoms/aqueous solution interface. I. Acid-base equilibria and spectroscopic observation of freshwater and marine species

This work reports on a concerted study of diatom-water interfaces for two marine planktonic (Thalassiosira weissflogii= TW, Skeletonema costatum= SC) and two freshwater periphytic species (Achnanthidium minutissimum= AMIN, Navicula minima= NMIN). Proton surface adsorption was measured at 25°C, pH of 3 to 11 and ionic strength of 0.001 to 1.0 M via potentiometric titration using a limited residence time reactor. Electrophoretic mobility of living cells and their frustules was measured as a function of pH and ionic strength. Information on the chemical composition and molecular structure of diatoms surfaces was obtained using FT-IR (in situ attenuated total reflectance) and X-ray Photoelectron Spectroscopy (XPS). The surface area of living cells and their frustules in aqueous solutions was quantified using Small Angle X-ray Scattering Spectroscopy (SAXS).These observations allowed us to identify the nature and to determine the concentration of the major surface functional groups (carboxyl, amine and silanol) responsible for the amphoteric behavior of cell surfaces in aqueous solutions. Taking into account the relative proportion of surface sites inferred from XPS and FT-IR measurements, a surface complexation model of diatom-solution interfaces was generated on the basis of surface titration results. The cell-normalized ratios of the three major surface sites {>COOH}: {>NH₃}: {>SiOH} are 1:1:0.1, 1:10:0, 1:1:0.4 and 1:1:0.3 for TW, SC, AMIN and NMIN, respectively. The total amount of proton/hydroxyl active surface sites for investigated species ranges from 1 (NMIN) to 9 (SC) mmol/g dry weight. Normalization of these site densities to the area of siliceous skeleton yields values between 0.3 (NMIN) and 0.9 mmol/m² (SC) which are an order of magnitude higher than corresponding values for organic-free frustules or amorphous silica. This suggests that the amphoteric properties and possibly the affinity for metal adsorption of diatom cultures are essentially controlled by the 3-D organic layers covering the silica frustule.     

Copper isotope fractionation during its interaction with soil and aquatic microorganisms and metal oxy(hydr)oxides: Possible structural control

This work is aimed at quantifying the main environmental factors controlling isotope fractionation of Cu during its adsorption from aqueous solutions onto common organic (bacteria, algae) and inorganic (oxy(hydr)oxide) surfaces. Adsorption of Cu on aerobic rhizospheric (Pseudomonas aureofaciens CNMN PsB-03) and phototrophic aquatic (Rhodobacter sp. f-7bl, Gloeocapsa sp. f-6gl) bacteria, uptake of Cu by marine (Skeletonema costatum) and freshwater (Navicula minima, Achnanthidium minutissimum and Melosira varians) diatoms, and Cu adsorption onto goethite (FeOOH) and gibbsite (AlOOH) were studied using a batch reaction as a function of pH, copper concentration in solution and time of exposure. Stable isotopes of copper in selected filtrates were measured using Neptune multicollector ICP-MS. Irreversible incorporation of Cu in cultured diatom cells at pH 7.5-8.0 did not produce any isotopic shift between the cell and solution (Δ^65/63Cu(solid-solution)) within ±0.2‰. Accordingly, no systematic variation was observed during Cu adsorption on anoxygenic phototrophic bacteria (Rhodobacter sp.), cyanobacteria (Gloeocapsa sp.) or soil aerobic exopolysaccharide (EPS)-producing bacteria (P. aureofaciens) in circumneutral pH (4-6.5) and various exposure times (3 min to 48 h): Δ⁶⁵Cu(solid-solution) = 0.0 ± 0.4‰. In contrast, when Cu was adsorbed at pH 1.8-3.5 on the cell surface of soil the bacterium P. aureofacienshaving abundant or poor EPS depending on medium composition, yielded a significant enrichment of the cell surface in the light isotope (Δ⁶⁵Cu (solid-solution) = −1.2 ± 0.5‰). Inorganic reactions of Cu adsorption at pH 4-6 produced the opposite isotopic offset: enrichment of the oxy(hydr)oxide surface in the heavy isotope with Δ⁶⁵Cu(solid-solution) equals 1.0 ± 0.25‰ and 0.78 ± 0.2‰ for gibbsite and goethite, respectively. The last result corroborates the recent works of Mathur et al. [Mathur R., Ruiz J., Titley S., Liermann L., Buss H. and Brantley S. (2005) Cu isotopic fractionation in the supergene environment with and without bacteria. Geochim. Cosmochim. Acta69, 5233-5246] and Balistrieri et al. [Balistrieri L. S., Borrok D. M., Wanty R. B. and Ridley W. I. (2008) Fractionation of Cu and Zn isotopes during adsorption onto amorhous Fe(III) oxyhydroxide: experimental mixing of acid rock drainage and ambient river water. Geochim. Cosmochim. Acta72, 311-328] who reported heavy Cu isotope enrichment onto amorphous ferric oxyhydroxide and on metal hydroxide precipitates on the external membranes of Fe-oxidizing bacteria, respectively.Although measured isotopic fractionation does not correlate with the relative thermodynamic stability of surface complexes, it can be related to their structures as found with available EXAFS data. Indeed, strong, bidentate, inner-sphere complexes presented by tetrahedrally coordinated Cu on metal oxide surfaces are likely to result in enrichment of the heavy isotope on the surface compared to aqueous solution. The outer-sphere, monodentate complex, which is likely to form between Cu²⁺ and surface phosphoryl groups of bacteria in acidic solutions, has a higher number of neighbors and longer bond distances compared to inner-sphere bidentate complexes with carboxyl groups formed on bacterial and diatom surfaces in circumneutral solutions. As a result, in acidic solution, light isotopes become more enriched on bacterial surfaces (as opposed to the surrounding aqueous medium) than they do in neutral solution.Overall, the results of the present study demonstrate important isotopic fractionation of copper in both organic and inorganic systems and provide a firm basis for using Cu isotopes for tracing metal transport in earth-surface aquatic systems. It follows that both adsorption on oxides in a wide range of pH values and adsorption on bacteria in acidic solutions are capable of producing a significant (up to 2.5-3‰ (±0.1-0.15‰)) isotopic offset. At the same time, Cu interaction with common soil and aquatic bacteria, as well as marine and freshwater diatoms, at 4 < pH < 8 yields an isotopic shift of only ±0.2-0.3‰, which is not related to Cu concentration in solution, surface loading, the duration of the experiment, or the type of aquatic microorganisms.     

Contrasting isotopic signatures between anthropogenic and geogenic Zn and evidence for post-depositional fractionation processes in smelter-impacted soils from Northern France

Zinc isotopes have been studied along two smelter-impacted soil profiles sampled near one of the largest Pb and Zn processing plants in Europe located in northern France, about 50 km south of Lille. Mean δ⁶⁶Zn values along these two soil profiles range from +0.22 ± 0.17‰ (2σ) to +0.34 ± 0.17‰ (2σ) at the lowest horizons and from +0.38 ± 0.45‰ (2σ) to +0.76 ± 0.14‰ (2σ) near the surface. The δ⁶⁶Zn values in the lowest horizons of the soils are interpreted as being representative of the local geochemical background (mean value +0.31 ± 0.38‰), whereas heavier δ⁶⁶Zn values near the surface of the two soils are related to anthropogenic Zn. This anthropogenic Zn occurs in the form of franklinite (ZnFe₂O₄)-bearing slag grains originating from processing wastes at the smelter site and exhibiting δ⁶⁶Zn values of +0.81 ± 0.20‰ (2σ). The presence of franklinite is indicated by EXAFS analysis of the topsoil samples from both soil profiles as well as by micro-XANES analysis of the surface horizon of a third smelter-impacted soil from a distant site. These results indicate that naturally occurring Zn and smelter-derived Zn exhibit significantly different δ⁶⁶Zn values, which suggests that zinc isotopes can be used to distinguish between geogenic and anthropogenic sources of Zn in smelter-impacted soils. In addition to a possible influence of additional past sources of light Zn (likely Zn-sulfides and Zn-sulfates directly emitted by the smelter), the light δ⁶⁶Zn values in the surface horizons compared to smelter-derived slag materials are interpreted as resulting mainly from fractionation processes associated with biotic and/or abiotic pedological processes (Zn-bearing mineral precipitation, Zn complexation by organic matter, and plant uptake of Zn). This conclusion emphasizes the need for additional Zn isotopic studies before being able to use Zn isotopes to trace sources and pathways of this element in surface environments.     

Fractionation of Cu and Zn isotopes during adsorption onto amorphous Fe(III) oxyhydroxide: Experimental mixing of acid rock drainage and ambient river water

Fractionation of Cu and Zn isotopes during adsorption onto amorphous ferric oxyhydroxide is examined in experimental mixtures of metal-rich acid rock drainage and relatively pure river water and during batch adsorption experiments using synthetic ferrihydrite. A diverse set of Cu- and Zn-bearing solutions was examined, including natural waters, complex synthetic acid rock drainage, and simple NaNO₃ electrolyte. Metal adsorption data are combined with isotopic measurements of dissolved Cu (⁶⁵Cu/⁶³Cu) and Zn (⁶⁶Zn/⁶⁴Zn) in each of the experiments. Fractionation of Cu and Zn isotopes occurs during adsorption of the metal onto amorphous ferric oxyhydroxide. The adsorption data are modeled successfully using the diffuse double layer model in PHREEQC. The isotopic data are best described by a closed system, equilibrium exchange model. The fractionation factors (α_soln-solid) are 0.99927 ± 0.00008 for Cu and 0.99948 ± 0.00004 for Zn or, alternately, the separation factors (Δ_soln-solid) are −0.73 ± 0.08‰ for Cu and −0.52 ± 0.04‰ for Zn. These factors indicate that the heavier isotope preferentially adsorbs onto the oxyhydroxide surface, which is consistent with shorter metal-oxygen bonds and lower coordination number for the metal at the surface relative to the aqueous ion. Fractionation of Cu isotopes also is greater than that for Zn isotopes. Limited isotopic data for adsorption of Cu, Fe(II), and Zn onto amorphous ferric oxyhydroxide suggest that isotopic fractionation is related to the intrinsic equilibrium constants that define aqueous metal interactions with oxyhydroxide surface sites. Greater isotopic fractionation occurs with stronger metal binding by the oxyhydroxide with Cu > Zn > Fe(II).     

Mo isotope fractionation during adsorption to Fe (oxyhydr)oxides

Molybdenum (Mo) isotopes have great potential as a paleoredox indicator, but this potential is currently restricted by an incomplete understanding of isotope fractionations occurring during key (bio)geochemical processes. To address one such uncertainty we have investigated the isotopic fractionation of Mo during adsorption to a range of Fe (oxyhydr)oxides, under variable Mo/Fe-mineral ratios and pH. Our data confirm that Fe (oxyhydr)oxides can readily adsorb Mo, highlighting the potential importance of this removal pathway for the global Mo cycle. Furthermore, adsorption of Mo to Fe (oxyhydr)oxides is associated with preferential uptake of the lighter Mo isotopes. Fractionations between the solid and dissolved phase (Δ⁹⁸Mo) increase at higher pH, and also vary with mineralogy, increasing in the order magnetite (Δ⁹⁸Mo = 0.83 ± 0.60‰) < ferrihydrite (Δ⁹⁸Mo = 1.11 ± 0.15‰) < goethite (Δ⁹⁸Mo = 1.40 ± 0.48‰) < hematite (Δ⁹⁸Mo = 2.19 ± 0.54‰). Small differences in isotopic fractionation are also seen at varying Mo/Fe-mineral ratios for individual minerals. The observed isotopic behaviour is consistent with both fractionation during adsorption to the mineral surface (a function of vibrational energy) and adsorption of different Mo species/structures from solution. The different fractionation factors determined for different Fe (oxyhydr)oxides suggests that these minerals likely exert a major control on observed natural Mo isotope compositions during sediment deposition beneath suboxic through to anoxic (but non-sulfidic) bottom waters. Our results confirm that Mo isotopes can provide important information on the spatial extent of different paleoredox conditions, providing they are used in combination with other techniques for evaluating the local redox environment and the mineralogy of the depositing sediments.     

Cadmium and lead interaction with diatom surfaces: A combined thermodynamic and kinetic approach

This work is devoted to the physico-chemical study of cadmium and lead interaction with diatom-water interfaces for two marine planktonic (Thalassiosira weissflogii, TW; Skeletonema costatum, SC) and two freshwater periphytic species (Achnanthidium minutissimum, AMIN; Navicula minima, NMIN) by combining adsorption measurements with surface complexation modeling. Adsorption kinetics was studied as a function of pH and initial metal concentration in sodium nitrate solution and in culture media. Kinetic data were consistent with a two-step mechanism in which the loss of a water molecule from the inner coordination sphere of the metal is rate limiting. Reversible adsorption experiments, with 3 h of exposure to metal, were performed as a function of pH (2-9), metal concentration in solution (10⁻⁹-10⁻³ M), and ionic strength (10⁻³-1.0 M). While the shape of pH-dependent adsorption edge is similar among all four diatom species, the constant-pH adsorption isotherm and maximal binding capacities differ. Measurements of electrophoretic mobilities (μ) revealed negative surface potential for AMIN diatom, however, the absolute value of μ decreases with increase of [Pb²⁺]_aq suggesting the metal adsorption on negative surface sites. These observations allowed us to construct a surface complexation model (SCM) for cadmium and lead binding by diatom surfaces that postulates the Constant Capacitance of the electric double layer and considers Cd and Pb complexation with mainly carboxylic and, partially, silanol groups. In the full range of investigated Cd concentration, the SCM is able to describe the concentration of adsorbed metal as a function of [Cd²⁺]_aq without implying the presence of high affinity, low abundance sites, that are typically used to model the metal interactions with natural multi-component organic substances. At the same time, Cd fast initial reaction requires the presence of “highly reactive sites” those concentration represents only 2.5-3% of the total amount of carboxylic sites. For reversible adsorption experiments, the dominating carboxylic groups, whose concentration is allowed to vary within the uncertainty of experimental acid-base titrations, are sufficient to reproduce the metal adsorption isotherms. Results of this study strongly suggest that laboratory experiments performed in a wide range of metal to biomass ratios, represent robust and relatively simple method for assessing the distribution of metals between aqueous solution and planktonic and periphytic biomass in natural settings.     

The geochemical behavior and isotopic composition of Hg in a mid-Pleistocene western Mediterranean sapropel

The concentrations of mercury (Hg) and other trace metals (Ni, Cu, Zn, Mo, Ba, Re, U) and the Hg isotopic composition were examined across a dramatic redox and productivity transition in a mid-Pleistocene Mediterranean Sea sapropel sequence. Characteristic trace metal enrichment in organic-rich layers was observed, with organic-rich sapropel layers ranging in Hg concentration from 314 to 488 ng/g (avg = 385), with an average enrichment in Hg by a factor of 5.9 compared to organic-poor background sediments, which range from 39 to 94 ng/g Hg (avg = 66). Comparison of seawater concentrations and sapropel accumulations of trace metals suggests that organic matter quantitatively delivers Hg to the seafloor. Near complete scavenging of Hg from the water column renders the sapropel Hg isotopic composition representative of mid-Pleistocene Mediterranean seawater. Sapropels have an average δ²⁰²Hg value of −0.91‰ ± 0.15‰ (n = 5, 1 SD) and Δ¹⁹⁹Hg value of 0.11‰ ± 0.03‰ (n = 5, 1 SD). Background sediments have an average δ²⁰²Hg of −0.76‰ ± 0.16‰ (n = 5, 1 SD) and Δ¹⁹⁹Hg of 0.05‰ ± 0.01‰ (n = 5, 1 SD), which is indistinguishable from the sapropel values. We suggest that the sapropel isotopic composition is most representative of the mid-Pleistocene Tyrrhenian Sea.     

A laser fluorination method for oxygen isotope analysis of biogenic silica and a new oxygen isotope calibration of modern diatoms in freshwater environments

An empirical calibration for the oxygen isotope fractionation between biogenic silica and water was determined for diatom frustules sampled from living diatom communities in the Jemez Mountains of northern New Mexico, USA. Over a temperature range from 5.1 to 37.8 °C, the silica-water fractionation is defined by the equation 1000 ln α_{(silica-water)} = 2.39(±0.13) × 10⁶T⁻² + 4.23(±1.49). This relationship is in close agreement with other published silica-water fractionation factors for laboratory cultured diatom samples; however, it is as much as 8‰ lower than equilibrium quartz-water fractionations and 3-4‰ lower than observed silica-water fractionations in diatomaceous silica collected from sediment traps and sediment cores. There are three possible explanations for the disparate silica-water fractionation factors observed in diatom silica: (1) silica does not precipitate in equilibrium with ambient water, (2) silica does precipitate in equilibrium with ambient water, but the silica-water fractionation factor for diatom silica is considerably less than the equilibrium fractionation factor for quartz-water, or (3) silica precipitation is influenced by a ‘vital’ effect, where the δ¹⁸O value of the water inside the diatom cell walls is lower than the δ¹⁸O values of ambient water.Post-mortem loss of organic material results in an alteration or ‘maturation’ of diatom silica in which silica reequilibrates with a silica-water fractionation closer to the equilibrium quartz-water fractionation. Alteration is likely to occur rapidly after the diatom frustule loses its organic coating, either as it settles through the water column or at the sediment-water interface; δ¹⁸O values recorded by paleo-diatom silica therefore do not record growing conditions but more likely record conditions at the sediment-water interface. In the case of lacustrine environments, where the bottom water remains at a nearly constant 4 °C, the reequilibration of diatom silica with bottom conditions could reduce or remove the conflating effects of temperature on δ¹⁸O values recorded by paleo-diatom silica and provide direct information on the δ¹⁸O value of the lake water.     

Magnesium-isotope fractionation during low-Mg calcite precipitation in a limestone cave - Field study and experiments

The chemical and isotopic composition of speleothem calcite and particularly that of stalagmites and flowstones is increasingly exploited as an archive of past environmental change in continental settings. Despite intensive research, including modelling and novel approaches, speleothem data remain difficult to interpret. A possible way foreword is to apply a multi-proxy approach including non-conventional isotope systems. For the first time, we here present a complete analytical dataset of magnesium isotopes (δ²⁶Mg) from a monitored cave in NW Germany (Bunker Cave). The data set includes δ²⁶Mg values of loess-derived soil above the cave (−1.0 ± 0.5‰), soil water (−1.2 ± 0.5‰), the carbonate hostrock (−3.8 ± 0.5‰), dripwater in the cave (−1.8 ± 0.2‰), speleothem low-Mg calcite (stalactites, stalagmites; −4.3 ± 0.6‰), cave loam (−0.6 ± 0.1‰) and runoff water (−1.8 ± 0.1‰) in the cave, respectively. Magnesium-isotope fractionation processes during weathering and interaction between soil cover, hostrock and solute-bearing soil water are non-trivial and depend on a number of variables including solution residence times, dissolution rates, adsorption effects and potential neo-formation of solids in the regolith and the carbonate aquifer. Apparent Mg-isotope fractionation between dripwater and speleothem low-Mg calcite is about 1000lnα_Mg-cc-Mg(aq) = −2.4‰. A similar Mg-isotope fractionation (1000lnα_Mg-cc-Mg(aq) ≈ −2.1‰) is obtained by abiogenic precipitation experiments carried out at aqueous Mg/Ca ratios and temperatures close to cave conditions. Accordingly, ²⁶Mg discrimination during low-Mg calcite formation in caves is highly related to inorganic fractionation effects, which may comprise dehydration of Mg²⁺ prior to incorporation into calcite, surface entrapment of light isotopes and reaction kinetics. Relevance of kinetics is supported by a significant negative correlation of Mg-isotope fractionation with the precipitation rate for inorganic precipitation experiments.     

Sources and biological fractionation of Silicon isotopes in the Eastern Equatorial Pacific

Silicon isotopes in dissolved silicic acid were measured in the upper four kilometers between 4°N and 3°S latitude at 110°W longitude in the eastern Equatorial Pacific. Silicon isotopes became progressively heavier with silicic acid depletion of surface water as expected from biological fractionation. The value of ε estimated by applying a steady-state isotope fractionation model to data from all stations between 4°N and 3°S was −0.77 ± 0.12‰ (std. err.). When the analysis was restricted to those stations whose temperature and salinity profiles indicated that they were directly influenced by upwelling of the Equatorial Undercurrent (EUC), the resulting value of ε was −1.08 ± 0.27‰ (std. err.) similar to the value established in culture studies (−1.1‰). When the non steady state Rayleigh model was applied to the same restricted data set the resulting value of ε was significantly more positive, −0.61 ± 0.16‰ (std. err.). To the extent that the equatorial system approximates a steady state these results support a value of −1.1‰ for the fractionation factor for isotopes of Si in the sea. Without the assumption of steady state the value of ε can only be constrained to be between −0.6 and −1.1‰. Silicic acid in Equatorial Pacific Deep Water below 2000 m had a near constant δ³⁰Si of +1.32 ± 0.05‰. That value is significantly more positive than obtained for North Pacific Deep Water at similar depths at stations to the northwest of our study area (0.9-1.0‰) and it is slightly less positive than new measures of the δ³⁰Si of silicic acid from the silicic acid plume centered over the Cascadia basin in the Northeast Pacific (Si(OH)₄ > 180  μM, δ³⁰Si = +1.46 ± 0.12‰ (SD, n = 4). We show that the data from the equator and Cascadia basin fit a general trend of increasing δ³⁰Si(OH)₄ with increasing silicic acid concentration in the deep sea, but that the isotope values from the Northeast Pacific are anomalously light. The observed level of variation in the silicon isotope composition of deep waters from this single ocean basin is considerably larger than that predicted by current models based on fractionation during opal formation with no isotope effect during dissolution. Confirmation of such high variability in deep water δ³⁰Si(OH)₄ within individual ocean basins will require reassessment of the mechanisms controlling the distribution of isotopes of silicon in the sea.     

A surface complexation model for cadmium and lead adsorption onto diatom surface

This work is devoted to the physico-chemical study of cadmium and lead interaction with diatom–water interfaces for two marine planktonic (Thalassiosira weissflogii = TW, Skeletonema costatum = SC) and two freshwater periphytic species (Achnanthidium minutissimum = AMIN, Navicula minima = NMIN) by combining adsorption measurements with surface complexation modeling. Reversible adsorption experiments were performed at 20 °C after 3 h of exposure as a function of pH, metal concentration in solution, and ionic strength. While the shape of pH-dependent adsorption edge is similar among all four diatom species, the constant-pH adsorption isotherm and maximal binding capacities differ. These observations allowed us to construct a surface complexation model for cadmium and lead binding by diatom surfaces that postulates the constant capacitance of the electric double layer and considers Cd and Pb complexation with mainly carboxylic and, partially, silanol groups. Parameters of this model are in agreement with previous acid–base titration results and allow quantitative reproduction of all adsorption experiments.     

Iron and magnesium isotopic compositions of peridotite xenoliths from Eastern China

We present high-precision measurements of Mg and Fe isotopic compositions of olivine, orthopyroxene (opx), and clinopyroxene (cpx) for 18 lherzolite xenoliths from east central China and provide the first combined Fe and Mg isotopic study of the upper mantle. δ⁵⁶Fe in olivines varies from 0.18‰ to −0.22‰ with an average of −0.01 ± 0.18‰ (2SD, n = 18), opx from 0.24‰ to −0.22‰ with an average of 0.04 ± 0.20‰, and cpx from 0.24‰ to −0.16‰ with an average of 0.10 ± 0.19‰. δ²⁶Mg of olivines varies from −0.25‰ to −0.42‰ with an average of −0.34 ± 0.10‰ (2SD, n = 18), opx from −0.19‰ to −0.34‰ with an average of −0.25 ± 0.10‰, and cpx from −0.09‰ to −0.43‰ with an average of −0.24 ± 0.18‰. Although current precision (∼±0.06‰ for δ⁵⁶Fe; ±0.10‰ for δ²⁶Mg, 2SD) limits the ability to analytically distinguish inter-mineral isotopic fractionations, systematic behavior of inter-mineral fractionation for both Fe and Mg is statistically observed: Δ⁵⁶Fe_ol-cpx = −0.10 ± 0.12‰ (2SD, n = 18); Δ⁵⁶Fe_ol-opx = −0.05 ± 0.11‰; Δ²⁶Mg_ol-opx = −0.09 ± 0.12‰; Δ²⁶Mg_ol-cpx = −0.10 ± 0.15‰. Fe and Mg isotopic composition of bulk rocks were calculated based on the modes of olivine, opx, and cpx. The average δ⁵⁶Fe of peridotites in this study is 0.01 ± 0.17‰ (2SD, n = 18), similar to the values of chondrites but slightly lower than mid-ocean ridge basalts (MORB) and oceanic island basalts (OIB). The average δ²⁶Mg is −0.30 ± 0.09‰, indistinguishable from chondrites, MORB, and OIB. Our data support the conclusion that the bulk silicate Earth (BSE) has chondritic δ⁵⁶Fe and δ²⁶Mg.The origin of inter-mineral fractionations of Fe and Mg isotopic ratios remains debated. δ⁵⁶Fe between the main peridotite minerals shows positive linear correlations with slopes within error of unity, strongly suggesting intra-sample mineral-mineral Fe and Mg isotopic equilibrium. Because inter-mineral isotopic equilibrium should be reached earlier than major element equilibrium via chemical diffusion at mantle temperatures, Fe and Mg isotope ratios of coexisting minerals could be useful tools for justifying mineral thermometry and barometry on the basis of chemical equilibrium between minerals. Although most peridotites in this study exhibit a narrow range in δ⁵⁶Fe, the larger deviations from average δ⁵⁶Fe for three samples likely indicate changes due to metasomatic processes. Two samples show heavy δ⁵⁶Fe relative to the average and they also have high La/Yb and total Fe content, consistent with metasomatic reaction between peridotite and Fe-rich and isotopically heavy melt. The other sample has light δ⁵⁶Fe and slightly heavy δ²⁶Mg, which may reflect Fe-Mg inter-diffusion between peridotite and percolating melt.     

Copper isotopic zonation in the Northparkes porphyry Cu-Au deposit, SE Australia

Significant, systematic Cu isotopic variations have been found in the Northparkes porphyry Cu-Au deposit, NSW, Australia, which is an orthomagmatic porphyry Cu deposit. Copper isotope ratios have been measured in sulfide minerals (chalcopyrite and bornite) by both solution and laser ablation multi-collector inductively coupled plasma-mass spectrometry (MC-ICP-MS). The results from both methods show a variation in δ⁶⁵Cu of hypogene sulfide minerals of greater than 1‰ (relative to NIST976). Significantly, the results from four drill holes through two separate ore bodies show strikingly similar patterns of Cu isotope variation. The patterns are characterized by a sharp down-hole decrease from up to 0.8‰ (0.29 ± 0.56‰, 1σ, n = 20) in the low-grade peripheral alteration zones (phyllic-propylitic alteration zone) to a low of ∼−0.4‰ (−0.25 ± 0.36‰, 1σ, n = 30) at the margins of the most mineralized zones (Cu grade >1 wt%). In the high-grade cores of the systems, the compositions are more consistent at around 0.2‰ (0.19 ± 0.14‰, 1σ, n = 40). The Cu isotopic zonation may be explained by isotope fractionation of Cu between vapor, solution and sulfides at high temperature, during boiling and sulfide precipitation processes. Sulfur isotopes also show an isotopically light shell at the margins of the high-grade ore zones, but these are displaced from the low δ⁶⁵Cu shells, such that there is no correlation between the Cu and S isotope signatures. Fe isotope data do not show any discernable variation along the drill core. This work demonstrates that Cu isotopes show a large response to high-temperature porphyry mineralizing processes, and that they may act as a vector to buried mineralization.     

Atmospheric deposition and isotope biogeochemistry of zinc in ombrotrophic peat

Zinc isotope ratios were measured in the top sections of dated ombrotrophic peat cores in Finland to investigate their potential as proxies for atmospheric sources and to constrain post depositional processes affecting the geochemical record. The peat deposits were located in Hietajärvi, a background site well away from any point pollution source and representing ‘background’ conditions, in Outokumpu, next to a mining site, and in Harjavalta, next to a smelter. Measured total concentrations, calculated excess concentrations and mass balance considerations suggest that zinc is subjected to important biogeochemical cycling within the peat. Significant isotopic variability was found in all three peat bogs, with heavier zinc in the deeper and lighter zinc in the upper sections. Isotope ratios and concentrations correlated in the two peats located next to dominant point sources, i.e. the smelting and mining site, suggesting that zinc isotopes trace pollution sources. Concentration and isotope peaks were offset from the period of mining and smelting activity, supporting migration of zinc down the profile. The δ⁶⁶Zn_JMC (where δ⁶⁶Zn = [(⁶⁶Zn/⁶⁴Zn)_sample/(⁶⁶Zn/⁶⁴Zn)_JMC-standard − 1] × 10³) of the top section sample at the remote Hietajärvi site was 0.9‰ and we suggest this represents the regional background isotope signature of atmospheric zinc. The deeper sections of the peat cores show isotopically heavier zinc than any potential atmospheric source, indicating that post depositional processes affected the isotopic records. The large variations encountered (up to 1.05‰ for δ⁶⁶Zn) and Rayleigh modelling imply that multiple fractionation of zinc during diagenetic alterations occurs and nutrient recycling alone cannot explain the fractionation pattern.We propose that zinc isotopes are amenable to identify different atmospheric zinc sources, including zinc derived from anthropogenic activities such as mining and smelting, but multiple biogeochemical processes seriously affect the record and they need to be evaluated and assessed carefully if zinc isotopes are used in terrestrial paleorecords.     

An experimental study of magnesium-isotope fractionation in chlorophyll-a photosynthesis

Measurements are presented of the magnesium isotopic composition of chlorophyll-a, extracted from cyanobacteria, relative to the isotopic composition of the culture medium in which the cyanobacteria were grown. Yields of 50-93% chlorophyll-a were achieved from the pigment extracts of Synechococcus elongatus, a unicellular cyanobacteria. This material was then digested using concentrated nitric acid to extract magnesium. Separation was accomplished using columns of cation-exchange resin, which achieved a 103 ± 10% yield of magnesium from chlorophyll-a. This procedure ensured accurate measurement of the magnesium-isotopic ratios without isobaric interferences using a multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS). We find a slight depletion in the heavier isotopes of magnesium in chlorophyll-a relative to culture medium, early growth phase: Δ²⁶Mg = −0.71(±0.35)‰ and Δ²⁵Mg = −0.37(±0.18)‰; late growth phase: Δ²⁶Mg = −0.53(±0.20)‰ and Δ²⁵Mg = −0.26(±0.11)‰, due to an apparent mass-dependent fractionation. We suggest that the small fractionation results from chelation during intracellular processes. A likely candidate for this chelation step involves the magnesium-chelatase enzyme, which mediates the insertion of magnesium to the tetrapyrrole ring during chlorophyll-a biosynthesis. Proof of this hypothesis can be tested with biological controls whereby steps in the enzymatic pathways of chlorophyll synthesis are selectively suppressed.     

Impact of soil weathering degree on silicon isotopic fractionation during adsorption onto iron oxides in basaltic ash soils, Cameroon

The sequestration of silicon in soil clay-sized iron oxides may affect the terrestrial cycle of Si. Iron oxides indeed specifically adsorb aqueous monosilicic acid (H₄SiO₄⁰), thereby influencing Si concentration in soil solution. Here we study the impact of H₄SiO₄⁰ adsorption on the fractionation of Si isotopes in basaltic ash soils differing in weathering degree (from two weathering sequences, Cameroon), hence in clay and Fe-oxide contents, and evaluate the potential isotopic impact on dissolved Si in surrounding Cameroon rivers. Adsorption was measured in batch experiment series designed as function of time (0-72 h) and initial concentration (ic) of Si in solution (0.61-1.18 mM) at 20 °C, constant pH (5.5) and ionic strength (1 mM). After various soil-solution contact times, the δ³⁰Si vs. NBS28 compositions were determined in selected solutions by MC-ICP-MS (Nu Plasma) in medium resolution, operating in dry plasma with Mg doping with an average precision of ±0.15‰ (±2σ_SEM). The quantitative adsorption of H₄SiO₄⁰ by soil Fe-oxides left a solution depleted in light Si isotopes, which confirms previous study on synthetic Fe-oxides. Measured against its initial composition (δ³⁰Si = +0.02 ± 0.07‰ (±2σ_SD)), the solutions were systematically enriched in ³⁰Si reaching maximum δ³⁰Si values ranging between +0.16‰ and +0.95‰ after 72 h contact time. The enrichment of the solution in heavy isotopes increased with increasing values of three parameters: soil weathering degree, iron oxide content, and proportion of short-range ordered Fe-oxide. The Si-isotopic signature of the solution was partly influenced by Si release, possibly through mineral dissolution and Si desorption from oxide surfaces, depending on soil type, highlighting the complex pattern of natural soils. Surrounding Cameroon rivers displayed a mean Si-isotopic signature of +1.19‰. Our data imply that in natural environments, H₄SiO₄⁰ adsorption by soil clay-sized Fe-oxides at least partly impacts the Si-isotopic signature of the soil solution exported to water streams.     

Application of iron and zinc isotopes to track the sources and mechanisms of metal loading in a mountain watershed

Here the hydrogeochemical constraints of a tracer dilution study are combined with Fe and Zn isotopic measurements to pinpoint metal loading sources and attenuation mechanisms in an alpine watershed impacted by acid mine drainage. In the tested mountain catchment, δ⁵⁶Fe and δ⁶⁶Zn isotopic signatures of filtered stream water samples varied by ∼3.5‰ and 0.4‰, respectively. The inherent differences in the aqueous geochemistry of Fe and Zn provided complimentary isotopic information. For example, variations in δ⁵⁶Fe were linked to redox and precipitation reactions occurring in the stream, while changes in δ⁶⁶Zn were indicative of conservative mixing of different Zn sources. Fen environments contributed distinctively light dissolved Fe (<−2.0‰) and isotopically heavy suspended Fe precipitates to the watershed, while Zn from the fen was isotopically heavy (>+0.4‰). Acidic drainage from mine wastes contributed heavier dissolved Fe (∼+0.5‰) and lighter Zn (∼+0.2‰) isotopes relative to the fen. Upwelling of Fe-rich groundwater near the mouth of the catchment was the major source of Fe (δ⁵⁶Fe ∼ 0‰) leaving the watershed in surface flow, while runoff from mining wastes was the major source of Zn. The results suggest that given a strong framework for interpretation, Fe and Zn isotopes are useful tools for identifying and tracking metal sources and attenuation mechanisms in mountain watersheds.     

Copper isotope fractionation in acid mine drainage

We measured the Cu isotopic composition of primary minerals and stream water affected by acid mine drainage in a mineralized watershed (Colorado, USA). The δ⁶⁵Cu values (based on ⁶⁵Cu/⁶³Cu) of enargite (δ⁶⁵Cu = −0.01 ± 0.10‰; 2σ) and chalcopyrite (δ⁶⁵Cu = 0.16 ± 0.10‰) are within the range of reported values for terrestrial primary Cu sulfides (−1‰ < δ⁶⁵Cu < 1‰). These mineral samples show lower δ⁶⁵Cu values than stream waters (1.38‰ ? δ⁶⁵Cu ? 1.69‰). The average isotopic fractionation (Δ_aq-min = δ⁶⁵Cu_aq − δ⁶⁵Cu_min, where the latter is measured on mineral samples from the field system), equals 1.43 ± 0.14‰ and 1.60 ± 0.14‰ for chalcopyrite and enargite, respectively. To interpret this field survey, we leached chalcopyrite and enargite in batch experiments and found that, as in the field, the leachate is enriched in ⁶⁵Cu relative to chalcopyrite (1.37 ± 0.14‰) and enargite (0.98 ± 0.14‰) when microorganisms are absent. Leaching of minerals in the presence of Acidithiobacillus ferrooxidans results in smaller average fractionation in the opposite direction for chalcopyrite (Δ_aq-min^o=-0.57±0.14‰, where min^o refers to the starting mineral) and no apparent fractionation for enargite (Δ_aq-min^o=0.14±0.14‰). Abiotic fractionation is attributed to preferential oxidation of ⁶⁵Cu⁺ at the interface of the isotopically homogeneous mineral and the surface oxidized layer, followed by solubilization. When microorganisms are present, the abiotic fractionation is most likely not seen due to preferential association of ⁶⁵Cu_aq with A. ferrooxidans cells and related precipitates. In the biotic experiments, Cu was observed under TEM to occur in precipitates around bacteria and in intracellular polyphosphate granules. Thus, the values of δ⁶⁵Cu in the field and laboratory systems are presumably determined by the balance of Cu released abiotically and Cu that interacts with cells and related precipitates. Such isotopic signatures resulting from Cu sulfide dissolution should be useful for acid mine drainage remediation and ore prospecting purposes.     

Copper isotope fractionation during surface adsorption and intracellular incorporation by bacteria

Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ⁶⁵Cu) to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5-6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ⁶⁵Cu_{solution-solid} = δ⁶⁵Cu_solution − δ⁶⁵Cu_solid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to −0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ⁶⁵Cu_{solution-solid} ranging from ∼+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ⁶⁵Cu of natural waters and soils is probably considerable.     

Nature of volatile depletion and genetic relationships in enstatite chondrites and aubrites inferred from Zn isotopes

Enstatite meteorites include the undifferentiated enstatite chondrites and the differentiated enstatite achondrites (aubrites). They are the most reduced group of all meteorites. The oxygen isotope compositions of both enstatite chondrites and aubrites plot along the terrestrial mass fractionation line, which suggests some genetic links between these meteorites and the Earth as well.For this study, we measured the Zn isotopic composition of 25 samples from the following groups: aubrites (main group and Shallowater), EL chondrites, EH chondrites and Happy Canyon (impact-melt breccia). We also analyzed the Zn isotopic composition and elemental abundance in separated phases (metal, silicates, and sulfides) of the EH4, EL3, and EL6 chondrites. The different groups of meteorites are isotopically distinct and give the following values (‰): aubrite main group (−7.08 < δ⁶⁶Zn < −0.37); EH3 chondrites (0.15 < δ⁶⁶Zn < 0.31); EH4 chondrites (0.15 < δ⁶⁶Zn < 0.27); EH5 chondrites (δ⁶⁶Zn = 0.27 ± 0.09; n = 1); EL3 chondrites (0.01 < δ⁶⁶Zn < 0.63); the Shallowater aubrite (1.48 < δ⁶⁶Zn < 2.36); EL6 chondrites (2.26 < δ⁶⁶Zn < 7.35); and the impact-melt enstatite chondrite Happy Canyon (δ⁶⁶Zn = 0.37).The aubrite Peña Blanca Spring (δ⁶⁶Zn = −7.04‰) and the EL6 North West Forrest (δ⁶⁶Zn = 7.35‰) are the isotopically lightest and heaviest samples, respectively, known so far in the Solar System. In comparison, the range of Zn isotopic composition of chondrites and terrestrial samples (−1.5 < δ⁶⁶Zn < 1‰) is much smaller ( [Luck et al., 2005] and [Herzog et al., 2009]).EH and EL3 chondrites have the same Zn isotopic composition as the Earth, which is another example of the isotopic similarity between Earth and enstatite chondrites. The Zn isotopic composition and abundance strongly support that the origin of the volatile element depletion between EL3 and EL6 chondrites is due to volatilization, probably during thermal metamorphism. Aubrites show strong elemental depletion in Zn compared to both EH and EL chondrites and they are enriched in light isotopes (δ⁶⁶Zn down to −7.04‰). This is the opposite of what would be expected if Zn elemental depletion was due to evaporation, assuming the aubrites started with an enstatite chondrite-like Zn isotopic composition. Evaporation is therefore not responsible for volatile loss from aubrites. On Earth, Zn isotopes fractionate very little during igneous processes, while differentiated meteorites show only minimal Zn isotopic variability. It is therefore very unlikely that igneous processes can account for the large isotopic fractionation of Zn in aubrites. Condensation of an isotopically light vapor best explains Zn depletion and isotopically light Zn in these puzzling rocks. Mass balance suggests that this isotopically light vapor carries Zn lost by the EL6 parent body during thermal metamorphism and that aubrites evolved from an EL6-like parent body. Finally, Zn isotopes suggest that Shallowater and aubrites originate from distinct parent bodies.