Bioleaching of Lizardite by Magnesium- and Nickel-Resistant Fungal Isolate from Serpentinite Soils—Implication for Carbon Capture and Storage

The major goal of this study was to evaluate the potential of fungal species indigenous to mine tailing soils in accelerating Mg release from lizardite (a polymorph of serpentine) at ambient T/P conditions. We characterized the culturable fungal isolates at three sampling sites representative of different degrees of mineral weathering by isolating the genomic subunits and internal transcribed spacer (ITS) rRNA genes using PCR and sequencing of cloned fragments. We chose the specific strain primarily identified as Talaromyces sp. for the further experiments with lizardite because of this strain's remarkable tolerance to high [Mg²⁺] (1 mol·L^?1) and [Ni²⁺] (10 mM·L^?1) levels in the screening test and its ubiquity in the most severely weathered samples. Results of dissolution experiments revealed that both magnesium-release rate and efficiency were significantly increased (e.g., by a factor of up to 15) in the presence of fungal cells than those in the abiotic controls. The enhanced dissolution of lizardite was mainly attributed to the fungal production of organic acids including oxalic acid, gluconic acid, formic acid, and fumaric acid added to the solution. The proton-promoted dissolution, however, was indicated not to be the only mechanism for fungus-lizardite interactions as much lesser Mg (in wt.%) was recovered in the abiotic system where the solution pH was constantly adjusted to match that of the fungal system. We also explored the dependence of fungal dissolution (of lizardite) on temperature and mineral particle sizes. In particular, we found that up to ～ 50 wt.% of Mg was released from mineral particles of ～ 50 μm within 30 days at 38°C, ～ 26% and 8% higher than that at 18°C and 28°C, respectively. At the same temperature of 28°C, the Mg-release efficiency increased from 12.2 wt% for particles of ～ 270 μm to 38.4 wt% for those of ～100 μm although no apparent difference was recognized when the particle size decreased below 100 μm. The nonlinear correlation of dissolution rates with particle surface areas suggested that the dissolution process was controlled by mineral surface-structural modification along with Mg release and by fungal cells’ interaction with these surface structures. An amorphous layer of Mg-depleted silica was detected at the reacted mineral surface by scanning electron microscopy (SEM) and Fourier transform infrared spectroscopy (FTIR). Formation of glushinskite (MgC₂O₄·2H₂O) was also observed when oxalate was accumulated to certain concentrations in the solution. Overall, this study showed that the isolated Talaromyces sp. was a promising bioagent to improve the efficacy of cation release from serpentine minerals for the purpose of carbon sequestration and resource recovery.     

An Experimental Investigation of the Effect of Bacillus megaterium on Apatite Dissolution

Field observations suggest that some mineral dissolution rates can be enhanced by microbial activity indirectly, without direct contact with the mineral surface. A series of apatite dissolution experiments was performed to better understand this rate enhancement process. Far-from equilibrium abiotic apatite dissolution rates, measured in mixed-flow reactors at 25°C were enhanced by increasing concentration of aqueous organic acids and decreasing aqueous phosphate activity, demonstrating the existence of indirect pathways for microbial rate enhancement. Further apatite dissolution experiments were performed in closed-system reactors in the presence of Bacillus megaterium , a common heterotrophic aerobe. Experiments were designed to allow the bacteria to be either in direct contact or indirect contact with the apatite; in the latter case, the microbes were physically separated from the apatite using dialysis bags. Apatite dissolution in indirect contact with Bacillus megaterium was 50 to 900% faster than abiotic controls. Bacterial rate enhancement was, however, 3 to over 10 times lower when Bacillus megaterium was in direct contract versus indirect contact with the apatite surfaces. These results show that (1) bacteria can accelerate rates without being in physical contact with the dissolving mineral, and (2) microbially mediated dissolution may be less effective when bacteria are in direct contact with mineral surfaces. Supression of mineral dissolution is interpreted to stem from the preferential colonization of reactive sites on the mineral surface.     

Magnesium isotope fractionation during microbially enhanced forsterite dissolution

Bacillus subtilis endospore‐mediated forsterite dissolution experiments were performed to assess the effects of cell surface reactivity on Mg isotope fractionation during chemical weathering. Endospores present a unique opportunity to study the isolated impact of cell surface reactivity because they exhibit extremely low metabolic activity. In abiotic control assays, ²⁴Mg was preferentially released into solution during forsterite dissolution, producing an isotopically light liquid phase (δ²⁶Mg = ?0.39 ± 0.06 to ?0.26 ± 0.09‰) relative to the initial mineral composition (δ²⁶Mg = ?0.24 ± 0.03‰). The presence of endospores did not have an apparent effect on Mg isotope fractionation associated with the release of Mg from the solid into the aqueous phase. However, the endospore surfaces preferentially adsorbed ²⁴Mg from the dissolution products, which resulted in relatively heavy aqueous Mg isotope compositions. These aqueous Mg isotope compositions increased proportional to the fraction of dissolved Mg that was adsorbed, with the highest measured δ²⁶Mg (?0.08 ± 0.07‰) corresponding to the highest degree of adsorption (~76%). The Mg isotope composition of the adsorbed fraction was correspondingly light, at an average δ²⁶Mg of ?0.49‰. Secondary mineral precipitation and Mg adsorption onto secondary minerals had a minimal effect on Mg isotopes at these experimental conditions. Results demonstrate the isolated effects of cell surface reactivity on Mg isotope fractionation separate from other common biological processes, such as metabolism and organic acid production. With further study, Mg isotopes could be used to elucidate the role of the biosphere on Mg cycling in the environment.     

The kinetics of siderophore‐mediated olivine dissolution

Silicate minerals represent an important reservoir of nutrients at Earth's surface and a source of alkalinity that modulates long‐term geochemical cycles. Due to the slow kinetics of primary silicate mineral dissolution and the potential for nutrient immobilization by secondary mineral precipitation, the bioavailability of many silicate‐bound nutrients may be limited by the ability of micro‐organisms to actively scavenge these nutrients via redox alteration and/or organic ligand production. In this study, we use targeted laboratory experiments with olivine and the siderophore deferoxamine B to explore how microbial ligands affect nutrient (Fe) release and the overall rate of mineral dissolution. Our results show that olivine dissolution rates are accelerated in the presence of micromolar concentrations of deferoxamine B. Based on the non‐linear decrease in rates with time and formation of a Fe³⁺‐ligand complex, we attribute this acceleration in dissolution rates to the removal of an oxidized surface coating that forms during the dissolution of olivine at circum‐neutral pH in the presence of O₂ and the absence of organic ligands. While increases in dissolution rates are observed with micromolar concentrations of siderophores, it remains unclear whether such conditions could be realized in natural environments due to the strong physiological control on microbial siderophore production. So, to contextualize our experimental results, we also developed a feedback model, which considers how microbial physiology and ligand‐promoted mineral dissolution kinetics interact to control the extent of biotic enhancement of dissolution rates expected for different environments. The model predicts that physiological feedbacks severely limit the extent to which dissolution rates may be enhanced by microbial activity, though the rate of physical transport modulates this limitation.     

Intracellular and Extracellular Biomineralization Induced by Klebsiella pneumoniae LH1 Isolated from Dolomites

Abstract

The interaction between bacteria and minerals is very complicated and has been intensively studied in the laboratory and the field in the last few decades, but the processes and mechanisms of biomineralization and mineral precipitation are still not fully understood and need to be explored further. In the present work, biomineralization experiments were undertaken using Klebsiella pneumoniae LH1, collected from a natural surface environment in an area of outcrops of Cambrian dolomite, in a culture medium with various Mg/Ca molar ratios (0, 3, 6 and 12). The mineral precipitates obtained were analyzed by X-ray diffraction (XRD), scanning electron microscope (SEM), energy dispersive spectrometer (EDS), Fourier transform infrared spectrometer (FTIR), laser scanning confocal microscopy (LSCM) and X-ray photoelectron spectroscopy (XPS). Cells were analyzed with a scanning transmission electron microscope (STEM), high resolution transmission electron microscope (HRTEM) and selected area electron diffraction (SAED). The composition of amino acids in extracellular polymeric substances (EPS) was also determined. In the experiments it was found that the production of ammonia and the presence of carbonate anhydrase promoted the increase of the medium pH and that minerals are nucleated on the EPS, which consist chiefly of amino acids and negatively-charged organic functional groups. With increasing Mg/Ca ratios, the mineral phases changed, including calcite (100%) at Mg/Ca molar ratio of 0, monohydrocalcite (36.05%) + dypingite (63.95%) at Mg/Ca molar ratio of 3, monohydrocalcite (29.72%) + dypingite (15.48%) + nesquehonite (54.80%) at Mg/Ca molar ratio of 6, and monohydrocalcite (14.2%) + dypingite (1.0%) + nesquehonite (84.80%) at Mg/Ca molar ratio of 12. Some intracellular amorphous calcium- and magnesium-rich inclusions were also detected in K. pneumoniae LH1, suggesting intracellular biomineralization accompanying the extracellular mineral precipitation. This study provides further understanding of the biomineralization processes of microorganisms.     

DIFFERENTIAL RESPONSES TO MAGNESIUM AND CALCIUM BY NATIVE POPULATIONS OF AGROPYRON SPICATUM

Plants of Agropyron spicatum (Pursh) Scribn. and Smith. from populations native to serpentine and nonserpentine soils were grown at varying levels of magnesium and calcium in culture solutions. The yields of plants from the two populations were different. At high Mg levels (low Ca) the yield of the serpentine population was significantly higher than that of the nonserpentine population. At low Mg the yield of the serpentine population leveled off at a Mg: Ca ratio of 1:2, while the yield of the nonserpentine population increased up to a Mg:Ca ratio of 1:8 and showed no leveling off. Chemical analyses of tissue showed that the Ca uptake of plants from the serpentine population was significantly higher than that of the nonserpentine population. In addition, the serpentine population maintained a lower Mg concentration in the shoots than the nonserpentine population at comparable Mg substrate levels. The two populations showed differences in Ca and Mg uptake efficiency and Mg/Ca, Ca + Mg/K + Na, and Ca + Mg + K + Na in the shoots. The ecotypic differentiation with respect to Mg and Ca between native populations of serpentine and nonserpentine A. spicatum does not appear to be due to any single mechanism but, rather, a combination of several possible mechanisms, i.e., differences in root morphology, uptake mechanisms, translocation of nutrients, and interactions between cations.     

Responses to Mg/Ca balance in an Iranian serpentine endemic plant, Cleome heratensis (Capparaceae) and a related non-serpentine species, C. foliolosa

A soil Ca/Mg quotient greater than unity is generally considered necessary for normal plant growth but some serpentine plants are adapted to much lower Ca/Mg quotients, resulting from a major cation imbalance in their substrata. In order to investigate the growth and tolerance responses of serpentine and non-serpentine species to varied Ca/Mg quotients, controlled nutrient solution experiments were performed using an a newly reported Iranian endemic serpentine plant, Cleome heratensis Bunge et Bien. Ex Boiss. and a related non-serpentine species Cleome foliolosa DC. and a Eurasian Ni-hyperaccumulating species Alyssum murale Waldst. and Kit. Seedlings were grown in modified Hoagland’s solutions with varying Ca and Mg concentrations (0.2–2.5 and 0.5–10 mM, respectively) in a fully factorial randomised block design. The yields of the two serpentine plants increased significantly as Mg concentrations in the nutrient solution were increased from 0.5 to 4 mM but decreased in the 10 mM Mg treatment. For C. foliolosa yields decreased significantly from 0.5 to 10 mM Mg, indicating the sensitivity of this non-serpentine plant, and the relative tolerance of the serpentine plants to extremely high levels of Mg. Shoot and root Mg and Ca concentrations in C. heratensis and A. murale were higher than those in C. foliolosa in the low and moderate Mg treatments, supporting the view that many serpentine plants have a relatively high requirement for Mg. Maximum Mg concentrations were found in the roots of C. heratensis. Yields of C. heratensis and A. murale did not change significantly as Ca levels in nutrient solution increased from 0.2 to 2.5 mM Ca, However the yield of C. foliolosa increased significantly from 0.2 to 1.5 mM Ca, indicating sensitivity in this non-serpentine plant and tolerance of the two serpentine plants to low levels of Ca correlated with tissue Ca concentrations, probably because of a greater ability for Ca uptake at low-Ca availability. Calcium deficiency in the low-Ca treatments could be a reason for reduced yield in the non-serpentine plants.     

“Bioshrouding”—a novel approach for securing reactive mineral tailings

A novel technique (“bioshrouding”) for safeguarding highly reactive sulfidic mineral tailings deposits is proposed. In this, freshly milled wastes are colonised with ferric iron-reducing heterotrophic acidophilic bacteria that form biofilms on reactive mineral surfaces, thereby preventing or minimising colonisation by iron sulfide-oxidising chemolithotrophs such as Acidithiobacillus ferrooxidans and Leptospirillum spp. Data from initial experiments showed that dissolution of pyrite could be reduced by between 57 and 75% by “bioshrouding” the mineral with three different species of heterotrophic acidophiles (Acidiphilium, Acidocella and Acidobacterium spp.), under conditions that were conducive to microbial oxidative dissolution of the iron sulfide.     

Microbial biomass and productivity in seagrass beds

This research focused on whether bacteria living in aerobic environments where Fe is often a limiting nutrient could access Fe associated with the clay mineral kaolinite. Kaolinite is one of the most abundant clays at the Earth's surface, and it often contains trace quantities of Fe as surface precipitates, accessory minerals, and structural substitutions. We hypothesized that aerobic bacteria may enhance kaolinite dissolution as a means of obtaining associated Fe. To test this hypothesis, we conducted microbial growth experiments in the presence of an aerobic Pseudomonas mendocina     

Serpentine and Nonserpentine Achillea millefolium Accessions Differ in Serpentine Substrate Tolerance and Response to Organic and Inorganic Amendments

Subgrade serpentine substrates are exceptionally difficult to revegetate due to multiple limitations including low N, P, and K, low Ca:Mg molar ratios, high levels of heavy metals including Ni, Cr, and Co, low organic matter, low CEC, and low water holding capacity. To examine the influence of plant origin on the success of the revegetation of serpentine substrates, granite and serpentine accessions of Achillea millefolium were grown on subgrade serpentine substrate amended with yard waste compost, slow-release NPK fertilizer, and/or CaSO₄ · 2H₂O (gypsum). The goals of this study were to: (1) identify the substrate amendment combination that maximized establishment of A. millefolium on serpentine substrate, (2) compare seedling establishment, survival, and growth of the serpentine and granite A. millefolium accessions in order to determine if a serpentine edaphic ecotype of A. millefolium exists and if this ecotype is superior to the granite accession for the establishment of vegetation on serpentine substrate and (3) if a serpentine edaphic ecotype of A. millefolium does exist, what physiological features with respect to mineral nutrition convey a higher tolerance of serpentine for this ecotype than the nonserpentine ecotype. Seedling establishment, survival, and growth were greatest for A. millefolium when the subgrade serpentine substrate was amended with 30% (v/v) compost and 220 mg kg substrate⁻¹ each of N, P, and K. The serpentine A. millefolium accession displayed a greater tolerance of the subgrade serpentine substrate, serpentine topsoil, and the amended subgrade serpentine substrate than the granite accession. Higher capacity of the serpentine A. millefolium accession for selective Ca translocation from roots to the shoot resulted in a significantly higher shoot Ca:Mg molar ratio than the granite accession and appeared to be the most important physiological feature conveying greater tolerance of the serpentine accession for serpentine substrates.     

A phytogeochemical survey of the flora of ultramafic and adjacent normal soils in North Morocco

Variation in plant elemental composition (Ni, Ca, Mg, Mg/Ca ratio) in relation to soil composition was investigated in a poorly studied ultramafic area in the north of Morocco. A total of 142 leaf samples representing 36 species from 9 sites (5 ultramafic and 4 normal soils from adjacent areas) were analysed. The soil was richer in Mg and Ni and had a higher Mg/Ca ratio in the ultramafic sites than in the control sites, and these differences were qualitatively reflected in the average mineral composition of the plants. However, there were considerable differences in mineral composition among species within serpentinic sites, indicating that species with contrasting mineral nutrition strategies can cope with the mineral element imbalance characteristic of ultramafic soils. Particularly noteworthy was the finding that species with high requirements of Ca are not excluded from serpentinic soils. In view of their high responsiveness to soil nickel and magnesium concentration, Dittrichia viscosa and Lavandula dentata are proposed as bioindicators of these elements in the soil in the Rif area. By contrast, two local serpentine endemics, Halimium atriplicifolium and Notholaena marantae were excluders of nickel and magnesium. This revised version was published online in August 2006 with corrections to the Cover Date.     

Surface alteration of realgar (As4S4) by Acidithiobacillus ferrooxidans

The chemical and physical characteristics of realgar (an arsenic sulfide mineral that occurs in several crystalline forms) in the presence of Acidithiobacillus ferrooxidans BY-3 were investigated in this work. Grains of the mineral were incubated for 10, 20, and 30 days with A. ferrooxidans cultured in 9K medium at 30 °C and at 150 rpm agitation. Abiotic control experiments were conducted in identical solutions. The effect of bioleaching on the surface properties of realgar was characterized by scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), inductively coupled plasma atomic emission spectroscope (ICP-AES), X-ray diffraction (XRD), and Raman spectroscopy. SEM and EDS analyses confirmed the ability of A. ferrooxidans to modify surfaces of realgar and to efficiently enhance its dissolution. ICP-AES showed the dissolution and precipitation of realgar during bioleaching. Based on the XRD pattern and the Raman spectra, the decrease in arsenic in the liquid phase was due to co-precipitation of the mineral with Fe(III) or Fe(III) compounds (e.g., jarosite or goethite). Thus, not only did Fe(III) alter the surface of realgar, but it also promoted its dissolution during bioleaching.     

Determining the impacts of fermentative bacteria on wollastonite dissolution kinetics

Silicate minerals can be a source of calcium and alkalinity, enabling CO₂ sequestration in the form of carbonates. For this to occur, the mineral needs to be first dissolved in an acidifying process such as the biological process of anaerobic fermentation. In the present study, the main factors which govern the dissolution process of an alkaline silicate mineral (wollastonite, CaSiO₃) in an anaerobic fermentation process were determined. Wollastonite dissolution kinetics was measured in a series of chemical batch experiments in order to be able to estimate the required amount of alkaline silicate that can neutralize the acidifying fermentation process. An anaerobic fermentation of glucose with wollastonite as the neutralizing agent was consequently performed in a fed-batch reactor. Results of this experiment were compared with an abiotic (control) fed-batch reactor in which the fermentation products (i.e. organic acids and alcohols) were externally supplied to the system at comparable rates and proportions, in order to provide chemical conditions similar to those during the biotic (fermentation) experiment. This procedure enabled us to determine whether dissolution of wollastonite was solely enhanced by production of organic acids or whether there were other impacts that fermentative bacteria could have on the mineral dissolution rate. The established pH profiles, which were the direct indicator of the dissolution rate, were comparable in both experiments suggesting that the mineral dissolution rate was mostly influenced by the quantity of the organic acids produced.     

Calcite and dolomite dissolution rates in the context of microbe–mineral surface interactions

Although microbes have been shown to alter the dissolution rate of carbonate minerals, a mechanistic understanding of the consequences of microbial surface colonization on carbonate dissolution has yet to be achieved. Here we report the use of vertical scanning interferometry (VSI) to study the effect of Shewanella oneidensis MR‐1 surface colonization on the dissolution rates of calcite (CaCO₃) and dolomite (CaMg(CO₃)₂) through qualitative analysis of etch pit development and quantitative measurements of surface‐normal dissolution rates. By quantifying and comparing the significant processes occurring at the microbe–mineral interface, the dominant mechanism of mineral dissolution during surface colonization was determined. MR‐1 attachment under aerobic conditions was found to influence carbonate dissolution through two distinct mechanistic pathways: (1) inhibition of carbonate dissolution through interference with etch pit development and (2) excavation of carbonate material at the cell–mineral interface during irreversible attachment to the mineral surface. The relative importance of these two competing effects was found to vary with the solubility of the carbonate mineral studied. For the faster‐dissolving calcite substrates, inhibition of dissolution by attachment and subsequent extracellular polysaccharide (EPS) production was the dominant effect associated with MR‐1 surface colonization. This interference with etch pit development resulted in a 40–70% decrease in the surface normal dissolution rate relative to cell‐free controls, depending primarily on the concentration of cells in solution. However, in the case of the slower‐dissolving dolomite substrates, carbonate material displaced during the entrenchment of cells on the surface far outweighed the abiotic dissolution rate. Therefore, during the initial stages of surface colonization, dolomite dissolution rates were actually enhanced by MR‐1 attachment. This study demonstrates the dynamic and competitive relationship between microbial surface colonization and mineral dissolution that may be expected to occur in natural environments.     

Ferrous ion oxidation by Thiobacillus ferrooxidans immobilized in calcium alginate

Summary Thiobacillus ferrooxidans was immobilized by entrapment into calcium alginate matrix. The immobilized bacteria were used in packed-bed column reactors for the continuous oxidation of ferrous ion at pH 1.5. The presence of mineral salts resulted in a shorter lag period before a steady-state of about 95% iron oxidation was achieved. Parallel shake flask experiments were used to evaluate pH, mineral salts, and alginate toxicity as factors influencing biological iron oxidation. Manometric experiments indicated that the previous growth history of T. ferrooxidans was important in determining the rate of iron oxidation. Scanning electron microscopy and energy dispersive analysis of X-rays were used to characterize bacteria entrapped in calcium alginate and the enrichment of iron in the matrix.     

Sulphate-reducing bacteria induce low-temperature Ca-dolomite and high Mg-calcite formation

In this study, we demonstrate that sulphate‐reducing bacteria induce anoxic low‐temperature Ca‐dolomite formation both in situ in Lagoa Vermelha and Brejo do Espinho, two neighbouring, dolomite‐precipitating hypersaline lagoons in Brazil, and in laboratory culture experiments. The metabolic activity of sulphate‐reducing bacteria facilitates dolomite formation under anoxic conditions, as demonstrated with experiments using dialysis bags. Overall changes in the chemical conditions of the medium exclusively, without the presence of bacteria, did not result in carbonate precipitation. Only pure cultures of metabolizing sulphate‐reducing bacteria induced Ca‐dolomite and high Mg‐calcite precipitates, indicating that the carbonate nucleation takes place in the locally changed microenvironment around the sulphate‐reducing bacterial cells. Not all pure strains, however, produced Ca‐dolomite under similar conditions, suggesting that the bacterial metabolism, activity and the rate of mineral precipitation have an influence on the type of carbonate formed.     

Comparison of growth characteristics and tolerance to serpentine soil of three ectomycorrhizal spruce seedlings in northern Japan

Picea glehnii is distributed widely on serpentine soils in northern Japan. Serpentine soil is characterised by the presence of heavy metals (Ni, Cr) and excessive Mg; these elements often suppress plant growth. We have examined the tolerance to serpentine soil and its effects on growth of P. glehnii, P. jezoensis (distributed in the same region) and P. abies (planted for timber production).The dry mass of each organ was not reduced in P. glehnii planted in serpentine soil contained nursery (serpentine nursery). In contrast, growth of P. jezoensis and P. abies was suppressed. Concentrations of Ni and Mg in needles and roots of P. glehnii planted in serpentine nursery were the lowest of the three species. Moreover, the photosynthetic rate of P. glehnii planted in the serpentine nursery was not reduced. P. glehnii has high capability to maintain low concentration of Ni, and ectomycorrhizal symbiosis may have a positive effect to excluding Ni. As a result, P. glehnii has a high tolerance against Ni toxicity, and its photosynthetic capacity is not suppressed by accumulation of Ni.     

Congeneric Serpentine and Nonserpentine Shrubs Differ More in Leaf Ca:Mg than in Tolerance of Low N, Low P, or Heavy Metals

Serpentine soils limit plant growth by NPK deficiencies, low Ca availability, excess Mg, and high heavy metal levels. In this study, three congeneric serpentine and nonserpentine evergreen shrub species pairs were grown in metalliferous serpentine soil with or without NPKCa fertilizer to test which soil factors most limit biomass production and mineral nutrition responses. Fertilization increased biomass production and allocation to leaves while decreasing allocation to roots in both serpentine and nonserpentine species. Simultaneous increases in biomass and leaf N:P ratios in fertilized plants of all six species suggest that N is more limiting than P in this serpentine soil. Neither N nor P concentrations, however, nor root to shoot translocation of these nutrients, differed significantly between serpentine and nonserpentine congeners. All six species growing in unfertilized serpentine soil translocated proportionately more P to leaves compared to fertilized plants, thus maintaining foliar P. Leaf Ca:Mg molar ratios of the nonserpentine species were generally equal to that of the soil. The serpentine species, however, maintained significantly higher leaf Ca:Mg than both their nonserpentine counterparts and the soil. Elevated leaf Ca:Mg in the serpentine species was achieved by selective Ca transport and/or Mg exclusion operating at the root-to-shoot translocation level, as root Ca and Mg concentrations did not differ between serpentine and nonserpentine congeners. All six species avoided shoot toxicity of heavy metals by root sequestration. The comparative data on nutrient deficiencies, leaf Ca:Mg, and heavy metal sequestration suggest that the ability to maintain high leaf Ca:Mg is a key evolutionary change needed for survival on serpentine soil and represents the physiological feature distinguishing the serpentine shrub species from their nonserpentine congeners. The results also suggest that high leaf Ca:Mg is achieved in these serpentine species by selective translocation of Ca and/or inhibited transport of Mg from roots, rather than by uptake/exclusion at root surfaces.     

Uptake of Trace Metals and Rare Earth Elements from Hornblende by a Soil Bacterium

Analysis of trace elements released from hornblende between pH 6.5 and 7.5 in the presence of Arthrobacter sp. shows that Fe, Ni, V, Mn, and, to a lesser extent, Co are preferentially released into solution relative to bacteria-free experiments. This enhanced release into solution could be due to contributions from the slightly lowered pH, the presence of low molecular weight organic acids (LMWOAs), or the presence of a catecholate siderophore in experiments with bacteria. The best explanation for enhanced metal release is siderophore complexation at the mineral surface followed by release to solution. However,the relative rates of metal release to solution in these experiments do not strictly follow the trend predicted by the relative ordering of metal hydrolysis, which might be predicted for siderophore-promoted dissolution. For some of these metals, release to solution is fast initially in biotic experiments, but concentrations in solution reach a steady state value or decrease with time as the bacteria cell numbers increase exponentially. Lack of enhanced release to solution for some metals and decreases in release rate with time for others may be explained by uptake into bacteria. Many of the metals predicted to strongly complex with siderophore (including Al, Ti, Fe, Cu) are heavily taken up into cellular material. The relative ordering of organic ligand-element complexation may therefore partially explain the relative ordering of uptake of trace metals and rare earth elements into cell material. Fractionation of heavy rare earth elements taken up into cellular material is also very strong, and increases from Ho to Lu. Strong fractionation in uptake of some elements by bacteria may create biological signatures either in the mineral substrate or in any mineral precipitates associated with the cellular material.