Ultrastructure, aggregation-state, and crystal growth of biogenic nanocrystalline sphalerite and wurtzite
-
John W. Moreau
,
Richard I. Webb
Abstract
In this study, we investigated the size, submicrometer-scale structure, and aggregation state of ZnS formed by sulfate-reducing bacteria (SRB) in a SRB-dominated biofilm growing on degraded wood in cold (T ~ 8 °C), circumneutral-pH (7.2−8.5) waters draining from an abandoned, carbonate-hosted Pb-Zn mine. High-resolution transmission electron microscope (HRTEM) data reveal that the earliest biologically induced precipitates are crystalline ZnS nanoparticles 1−5 nm in diameter. Although most nanocrystals have the sphalerite structure, nanocrystals of wurtzite are also present, consistent with a predicted size dependence for ZnS phase stability. Nearly all the nanocrystals are concentrated into 1−5 μm diameter spheroidal aggregates that display concentric banding patterns indicative of episodic precipitation and flocculation. Abundant disordered stacking sequences and faceted, porous crystalaggregate morphologies are consistent with aggregation-driven growth of ZnS nanocrystals prior to and/or during spheroid formation. Spheroids are typically coated by organic polymers or associated with microbial cellular surfaces, and are concentrated roughly into layers within the biofilm.
Size, shape, structure, degree of crystallinity, and polymer associations will all impact ZnS solubility, aggregation and coarsening behavior, transport in groundwater, and potential for deposition by sedimentation. Results presented here reveal nanometer- to micrometer-scale attributes of biologically induced ZnS formation likely to be relevant to sequestration via bacterial sulfate reduction (BSR) of other potential contaminant metal(loid)s, such as Pb2+, Cd2+, As3+ and Hg2+, into metal sulfides. The results highlight the importance of basic mineralogical information for accurate prediction and monitoring of long-term contaminant metal mobility and bioavailability in natural and constructed bioremediation systems. Our observations also provoke interesting questions regarding the role of size-dependent phase stability in biomineralization and provide new insights into the origin of submicrometer- to millimeter-scale petrographic features observed in low-temperature sedimentary sulfide ore deposits.
© 2015 by Walter de Gruyter Berlin/Boston
Articles in the same Issue
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Articles in the same Issue
- Hydroxyl in omphacites and omphacitic clinopyroxenes of upper mantle to lower crustal origin beneath the Siberian platform
- Structural variations induced by difference of the inert pair effect in the stibnite-bismuthinite solid solution series (Sb,Bi)2S3
- Hydrogen solubility and speciation in natural, gem-quality chromian diopside
- Ultrastructure, aggregation-state, and crystal growth of biogenic nanocrystalline sphalerite and wurtzite
- Impactite from Henbury, Australia
- Neutron and synchrotron X-ray diffraction study of the structures and dehydration behaviors of ramsdellite and “groutellite”
- Hydrothermal synthesis and crystal chemistry of the new strontium uranyl selenites, Sr[(UO2)3(SeO3)2O2]⋅4H2O and Sr[UO2(SeO3)2]
- Study of cation order-disorder in MgAl2O4spinel by in situ neutron diffraction up to 1600 K and 3.2 GPa
- Magnetic granulometry from equilibrium magnetization measurements: Mineral magnetometry of superparamagnetic particles and application to synthetic ferrihydrites
- Hydroxide in kyanite: A quantitative determination of the absolute amount and calibration of the IR spectrum
- Analysis of uranyl-bearing phases by EXAFS spectroscopy: Interferences, multiple scattering, accuracy of structural parameters, and spectral differences
- X-ray diffraction evidence for a monoclinic form of stibnite, Sb2S3, below 290 K
- Sulfur species at chalcopyrite (CuFeS2) fracture surfaces
- Dehydration and rehydration process in boggsite: An in situ X-ray single-crystal study
- Empressite, AgTe, from the Empress-Josephine mine, Colorado, U.S.A.: Composition, physical properties, and determination of the crystal structure
- Correlation of pH-dependent surface interaction forces to amino acid adsorption: Implications for the origin of life
- A near-infrared spectroscopic study of hydroxyl in natural chondrodite
- High-pressure elasticity of a natural magnetite crystal
- Isotopic and chemical alteration of zircon by metamorphic fluids: U-Pb age depth-profiling of zircon crystals from Barrowʼs garnet zone, northeast Scotland
- A novel approach to determine high-pressure high-temperature fluid and melt compositions using diamond-trap experiments
- Lindbergite, a new Mn oxalate dihydrate from Boca Rica mine, Galiléia, Minas Gerais, Brazil, and other occurrences
- Pyrophyllite dehydroxylation process by First Principles calculations
- Plagioclase from planetary basalts: Chemical signatures that reflect planetary volatile budgets, oxygen fugacity, and styles of igneous differentiation
- The structure of the manganese oxide on the sheath of the bacterium Leptothrix discophora: An XAFS study
- An X-ray Rietveld study of piemontite on the join Ca2Al3Si3O12(OH)–Ca2Mn33+Si3O12(OH) formed by hydrothermal synthesis
- Raman spectroscopy of basic copper(II) and some complex copper(II) sulfate minerals: Implications for hydrogen bonding
- Incorporation of sodium into the chlorite structure: the crystal structure of glagolevite, Na(Mg,Al)6[Si3AlO10](OH,O)8
- Cation disorder in dolomite, CaMg(CO3)2, and its influence on the aragonite + magnesite ↔ dolomite reaction boundary
