Nanospectroscopy Captures Nanoscale Compositional Zonation in Barite Solid Solutions

Scientists have long suspected that compositionally zoned particles can form under far-from equilibrium precipitation conditions, but their inferences have been based on bulk solid and solution measurements. We are the first to directly observe nanoscale trace element compositional zonation in <10 µm-sized particles using X-ray fluorescence nanospectroscopy at the Hard X-ray Nanoprobe (HXN) Beamline at National Synchrotron Light Source II (NSLS-II). Through high-resolution images, compositional zonation was observed in barite (BaSO4) particles precipitated from aqueous solution, in which Sr2+ cations as well as HAsO42− anions were co-precipitated into (Ba,Sr)SO4 or Ba(SO4,HAsO4) solid solutions. Under high salinity conditions (NaCl ≥ 1.0 M), bands contained ~3.5 to ~5 times more trace element compared to the center of the particle formed in early stages of particle growth. Quantitative analysis of Sr and As fractional substitution allowed us to determine that different crystallographic growth directions incorporated trace elements to different extents. These findings provide supporting evidence that barite solid solutions have great potential for trace element incorporation; this has significant implications for environmental and engineered systems that remove hazardous substances from water.

[1]  K. N. Dollman,et al.  - 1 , 1743 .

[2]  V. Goldschmidt.  Atlas der Krystallformen , 1913 .

[3]  H. Doerner,et al.  CO-PRECIPITATION OF RADIUM AND BARIUM SULFATES1 , 1925 .

[4]  PRECIPITATION FROM HOMOGENEOUS SOLUTION , 1952 .

[5]  L. Gordon,et al.  Distribution of Strontium within Barium Sulfate Precipitated from Homogeneous Solution , 1954 .

[6]  D. Skoog.  Fundamentals of analytical chemistry , 1963 .

[7]  C. Blount.  Barite solubilities and thermodynamic quantities up to 300 degrees C and 1400 bars , 1977 .

[8]  S. Saxena,et al.  Kinetics and equilibrium in mineral reactions , 1983 .

[9]  T. Loomis.  Compositional Zoning of Crystals: A Record of Growth and Reaction History , 1983 .

[10]  E. Reardon,et al.  Celestite (SrSO4(s)) solubility in water, seawater and NaCl solution , 1987 .

[11]  L. N. Plummer,et al.  Thermodynamics of aragonite-strontianite solid solutions: Results from stoichiometric solubility at 25 and 76°C , 1987 .

[12]  L. N. Plummer,et al.  Reaction paths and equilibrium end-points in solid-solution aqueous-solution systems , 1990 .

[13]  P. Glynn,et al.  Solid-solution aqueous-solution equilibria; thermodynamic theory and representation , 1990 .

[14]  P. Glynn.  Modeling solid-solution reactions in low-temperature aqueous systems , 1990 .

[15]  L. Fernández-Díaz,et al.  Experimentally produced oscillatory zoning in the (Ba, Sr)SO4 solid solution , 1992, Nature.

[16]  L. Fernández-Díaz,et al.  Crystallization of solid solutions from aqueous solutions in a porous medium: zoning in (Ba, Sr)SO4 , 1993, Geological Magazine.

[17]  D. Lashof,et al.  The Environmental Perspective , 1996 .

[18]  G. Waychunas,et al.  Oxyanion Behavior in Alkaline Environments: Sorption and Desorption of Arsenate in Ettringite , 1997 .

[19]  L. Fernández-Díaz,et al.  Nucleation, growth, and zoning phenomena in crystallizing (Ba,Sr)CO3, Ba(SO4,CrO4), (Ba,Sr)SO4, and (Cd,Ca)CO3 solid solutions from aqueous solutions , 1997 .

[20]  F. Millero,et al.  A Chemical Equilibrium Model for Natural Waters , 1998 .

[21]  E. Curti.  Coprecipitation of radionuclides with calcite: estimation of partition coefficients based on a review of laboratory investigations and geochemical data , 1999 .

[22]  A. Putnis,et al.  The composition of solid solutions crystallising from aqueous solutions: the influence of supersaturation and growth mechanisms , 2000 .

[23]  A. Putnis,et al.  Direct calculation of thermodynamic properties of the barite/celestite solid solution from molecular principles , 2000 .

[24]  Pierre D. Glynn,et al.  Solid-solution solubilities and thermodynamics: Sulfates, carbonates and halides , 2000 .

[25]  A. Putnis,et al.  Barite scale formation and dissolution at high ionic strength studied with atomic force microscopy , 2001 .

[26]  P. Fenter,et al.  Structure of Barite (001)− and (210)−Water Interfaces , 2001 .

[27]  R. Ford.  Rates of hydrous ferric oxide crystallization and the influence on coprecipitated arsenate. , 2002, Environmental science & technology.

[28]  I. L'Heureux,et al.  A model of oscillatory zoning in solid solutions grown from aqueous solutions: Applications to the (Ba,Sr)SO 4 system , 2002 .

[29]  A. Putnis,et al.  The kinetics of nucleation of solid solutions from aqueous solutions: A new model for calculating non-equilibrium distribution coefficients , 2002 .

[30]  D. Bejan,et al.  Removal of arsenic from synthetic acid mine drainage by electrochemical pH adjustment and coprecipitation with iron hydroxide. , 2003, Environmental science & technology.

[31]  E. Watson,et al.  A conceptual model for near-surface kinetic controls on the trace-element and stable isotope composition of abiogenic calcite crystals , 2004 .

[32]  Harry Y. McSween,et al.  Accuracy of plagioclase compositions from laboratory and Mars spacecraft thermal emission spectra , 2004 .

[33]  Barry Lai,et al.  Elemental and Redox Analysis of Single Bacterial Cells by X-ray Microbeam Analysis , 2004, Science.

[34]  Yinian Zhu,et al.  Solubility and stability of barium arsenate and barium hydrogen arsenate at 25 °C , 2005 .

[35]  L. Fernández-Díaz,et al.  Relationships between crystal morphology and composition in the (Ba,Sr)SO4–H2O solid solution–aqueous solution system , 2006 .

[36]  I. L'Heureux,et al.  Oscillatory zoning in a (Ba,Sr)SO4 solid solution: Macroscopic and cellular automata models , 2006 .

[37]  F. Brandt,et al.  Thermodynamic properties and crystal growth behavior of the hashemite (BaSO4–BaCrO4) solid solution , 2006 .

[38]  A. Putnis,et al.  The effect of specific background electrolytes on water structure and solute hydration: Consequences for crystal dissolution and growth , 2008 .

[39]  Yasushi Yoshida,et al.  Partition coefficients of Ra and Ba in calcite , 2008 .

[40]  M. Prieto.  Thermodynamics of Solid Solution-Aqueous Solution Systems , 2009 .

[41]  Practical Application of Synchrotron-Based Hard X-Ray Microprobes in Soil Sciences , 2010 .

[42]  C. Noguera,et al.  Simulation of the nucleation and growth of binary solid solutions in aqueous solutions , 2010 .

[43]  J. Ganor,et al.  Co-precipitation of radium in high ionic strength systems: 1. Thermodynamic properties of the Na–Ra–Cl–SO4–H2O system – Estimating Pitzer parameters for RaCl2 , 2011 .

[44]  M. Zhang,et al.  Synthesis and surface properties of submicron barium sulfate particles , 2011 .

[45]  J. Ganor,et al.  Co-precipitation of radium in high ionic strength systems: 2. Kinetic and ionic strength effects , 2011 .

[46]  Fenglian Fu,et al.  Removal of heavy metal ions from wastewaters: a review. , 2011, Journal of environmental management.

[47]  A. Stack,et al.  Calcite Growth Rates As a Function of Aqueous Calcium-to-Carbonate Ratio, Saturation Index, and Inhibitor Concentration: Insight into the Mechanism of Reaction and Poisoning by Strontium , 2012 .

[48]  C. Noguera,et al.  A Theoretical Treatment of the Precipitation of Doubly Substituted Solid Solutions in Aqueous Solutions , 2012 .

[49]  Li Li,et al.  11 nm hard X-ray focus from a large-aperture multilayer Laue lens , 2013, Scientific Reports.

[50]  Wei Liu,et al.  CORRIGENDUM: Biodegradation-inspired bioproduction of methylacetoin and 2-methyl-2,3-butanediol , 2013, Scientific Reports.

[51]  Jörg Maser,et al.  Quantitative x-ray phase imaging at the nanoscale by multilayer Laue lenses , 2013, Scientific Reports.

[52]  R. Hammack,et al.  Co-precipitation of radium with barium and strontium sulfate and its impact on the fate of radium during treatment of produced water from unconventional gas extraction. , 2014, Environmental science & technology.

[53]  Radisav D. Vidic,et al.  Kinetics and Equilibrium of Barium and Strontium Sulfate Formation in Marcellus Shale Flowback Water , 2014 .

[54]  Robert G. Arnold,et al.  Research on phosphatis by Kang and Noguera , 2014 .

[55]  Nathalie Bouet,et al.  Hard x-ray nanofocusing by multilayer Laue lenses , 2014 .

[56]  R. Hammack,et al.  Fate of Radium in Marcellus Shale Flowback Water Impoundments and Assessment of Associated Health Risks. , 2015, Environmental science & technology.

[57]  S Kalbfleisch,et al.  Pushing the limits: an instrument for hard X-ray imaging below 20 nm. , 2015, Journal of synchrotron radiation.

[58]  J. Godinho,et al.  Growth Kinetics and Morphology of Barite Crystals Derived from Face-Specific Growth Rates , 2015 .

[59]  HeCan,et al.  Impact of Antiscalants on the Fate of Barite in the Unconventional Gas Wells , 2016 .

[60]  Li Li,et al.  Multimodality hard-x-ray imaging of a chromosome with nanoscale spatial resolution , 2016, Scientific Reports.

[61]  F. Brandt,et al.  Nano-structural features of barite crystals observed by electron microscopy and atom probe tomography , 2016 .

[62]  M. Prieto,et al.  Crystallization behavior of solid solutions from aqueous solutions: An environmental perspective , 2016 .

[63]  T. Uruga,et al.  Application of arsenic in barite as a redox indicator for suboxic/anoxic redox condition , 2016 .

[64]  M. Cecchini,et al.  Ultrastructural Characterization of the Lower Motor System in a Mouse Model of Krabbe Disease , 2016, Scientific Reports.

[65]  Claudia Felser,et al.  Berry phase and band structure analysis of the Weyl semimetal NbP , 2016, Scientific Reports.

[66]  Y S Chu,et al.  Design and performance of an X-ray scanning microscope at the Hard X-ray Nanoprobe beamline of NSLS-II. , 2017, Journal of synchrotron radiation.

[67]  F. Brandt,et al.  Retention of 226 Ra by barite: The role of internal porosity , 2017 .

[68]  Hanfei Yan,et al.  PyXRF: Python-based X-ray fluorescence analysis package , 2017, Optical Engineering + Applications.

[69]  A. Ghahreman,et al.  Review of arsenic metallurgy: Treatment of arsenical minerals and the immobilization of arsenic , 2017 .

[70]  M. Gomez,et al.  A qualitative and quantitative investigation of partitioning and local structure of arsenate in barite lattice during coprecipitation of barium, sulfate, and arsenate , 2017 .

[71]  F. Brandt,et al.  Thermodynamics of the solid solution - Aqueous solution system (Ba,Sr,Ra)SO 4 + H 2 O: I. The effect of strontium content on radium uptake by barite , 2018 .

[72]  野村栄一,et al.  2 , 1900, The Hatak Witches.

[73]  E. Yuliwati,et al.  A Review , 2019, Current Trends and Future Developments on (Bio-) Membranes.

[74]  G. Fitzgerald,et al.  'I. , 2019, Australian journal of primary health.