Incorporation of metals into calcite in a deep

Transcription

1 Supporting information Incorporation of metals into calcite in a deep anoxic granite aquifer Henrik Drake, Frédéric A. Mathurin, Thomas Zack, Thorsten Schäfer, Nick MW Roberts, Martin Whitehouse, Andreas Karlsson, Curt Broman, Mats E. Åström Number of pages: 10, figures: 8, tables: 6 S1

2 X-ray diffraction method description. A representative number of crystals were picked (30-40) and pulverized in an agate mortar and placed on a background free sample holder made out of silicon metal. X-ray powder diffraction data were recorded in a PANalytical X'Pert 3 Powder diffractometer system (Cu K α1 -radiation) operated at 40 ma and 45 kv. The data was collected between 5 to 70 2θ for 20 minutes with an X Celerator strip detector to validate if there were any other minerals present. Background, peak searching and search & matchoperations were performed using HighScorePlus (3.03e) and the patterns were matched to reference patterns (ICSD for calcite and ICSD for lizardite 1T). S2

3 Supporting figures and tables Intensity (counts) Position [ 2Theta ] (Copper) Figure S1. XRD spectra of calcite from the four borehole sections, combined above (HD22112= B:1, HD22125=A:4, HD22134=A:2, HD:22132=A:3), and comparison of HD22134 with the calcite standard below, showing 100% match. In samples 22125, and there is one unmatched peak at roughly θ which corresponds to the K-β peak of the 100% peak of calcite positioned at θ. S3

4 Figure S2. Evolution of the fracture concentrations of (a) Cl and (b) Ca, and molar Me/Ca concentration ratios of (c) Mn, (d) Mg, (e) Sr and (f) Fe in boreholes A and B. In (c, d, f) ratios from B:1 are on the right y- axis and A:3, A:4 on the left y-axis for better readability. For A:2, no full trace element concentrations prior to 2012 exist. S4

5 Figure S3. Me/Ca molar concentration ratios (on the y-axis) in stagnant and fracture of the different borehole sections at three different time intervals (x-axis) to observe any systematic influence of the processes in the stagnant, such as precipitation, corrosion, sulfate reduction and colloid formation (see details in a : Fracture in November 2011 [for A:2 no sampling was done in 2011 and the 2012 fracture data were used instead, also for Ba, La and Y in A:4 and Ba in B:1, due to lack of these metals in the 2011 measurement]; 2: Stagnant in February 2012, when the instrumentation was extracted; 3: Fracture in November 2013 [B:1 and A:3] or April 2014 [A:2 and A:4], this was done well after the instrumentation was re-installed in the boreholes in 2012; 4: Stagnant in November 2011; 5: Fracture in November 2011; 6: Stagnant in November 2015). S5

6 Figure S4. Section specific trace element composition of calcite. Example of Sr vs Mg. Sections A:3 and A:4 have relatively similar compositions, which is also reflected in the calcite chemistry. S1

7 Figure S5. Transects within calcites from section A:2, with growth direction from left to right showing decrease in Li, Ba and Na, and highly variable La and a general but spiky trend of increasing Mn and Fe. S2

8 Figure S6. Water extraction episodes of the borehole sections (above) and corresponding number of precipitation episodes highlighted in calcite crystals (below). These zones were targeted with LA-ICP-MS. For B:1, the overgrowths were too fine-grained and discrete to track with individual LA-ICP-MS spots. See also Fig. 2 in the main text for examples of overgrowths. Diagram modified from Drake et al 1. S3

9 Figure S7. LA-ICP-MS trace element maps of three calcite crystals from borehole section A:4, showing elements Ba, Sr, Fe, La, Y, Mg, Mn and U. Maps from one more crystal and maps for Cu, V, Dy, Th, Cu, Mo, Nd, and Yb are available are deposited in a data archive and can be extracted on request. The maps have been masked to avoid the epoxy around the crystals. S4

10 Figure S8. δ 13 C (a) and δ 18 O (b) calculated for the fracture (2012) and stagnant (2012), and measured for the calcite (bulk samples and in situ analyses for δ 13 C). For the s, fractionation factors from 2 and 3 to calculate the hypothetical stable isotope composition of the from which the calcites precipitated. For δ 18 O, bars indicate the variation of the stable isotope composition over time in the s, and the temperature variation 1. (c) Selected δ 13 C transects from microanalyses from the crystals in (d) and (e), growth direction is from left to right. (d) Microscope image from the Cameca SIMS-instrument, showing calcite from A:2 with location of four 10 µm microanalyses within three growth zones (the oldest one is missing, to the left of 1 ). (e) Calcite from A:3 showing location of four microanalyses and ten growth zones. S5

11 Supplementary tables Tables S1-S3 and S5-S6 are given in an xlsx-file and Table S4 on partition coefficients is shown below. In the xlsx-file are: Table S1: Standards for calcite analyses Table S2: Ground data Table S3: Trace element data for calcite Table S5: Aquatic speciation modelling Table S6: Calcite δ 13 C and δ 18 O values S6

12 Table S4. Calculated p Me from borehole sections A:2, A:3, A:4, and B:1, divided into stagnant and fracture. Previously published laboratory data are shown for comparison. Metal A:2* A:3** A:4*** Stagnant Fracture Stagnant Fracture Stagnant p Me p Me p Me p Me p Me p Me p Me p Me p Me min) (max) (min) (max) (min) (max) (min) (max) (min) p Me (max) Fracture p Me (min) p Me (max) B:1**** Reference values Stagnant Fracture p Me p Me p Me p Me (min) (max) (min) (max) Laboratory data Li Na , 5 Mg Mn Fe Sr , 13, , Y Ba , 22, La Ce Pr Nd Sm Gd Dy Er Yb Cs U * Ionic strength: M; ph: ** Ionic strength: M; ph: *** Ionic strength: M; ph: # 25, for UO 2+ 2 (not determined for U(IV). S7

13 **** Ionic strength: M; ph: # Sorption data. No co-precipitation data available to the best of our knowledge. S8

14 References to the supporting information 1. Drake, H.; Tullborg, E.-L.; Sandberg, B.; Blomfeldt, T.; Åström., M. E., Extreme fractionation and micro-scale variation of sulphur isotopes during bacterial sulphate reduction in Deep ground systems. Geochimica et Cosmochimica Acta 2015, 161, Emrich, K.; Ehhalt, D. H.; Vogel, J. C., Carbon isotope fractionation during the precipitation of calcium carbonate. Earth and Planetary Science Letters 1970, 8, (5), Kim, S.-T.; O'Neil, J. R., Equilibrium and nonequilibrium oxygen isotope effects in synthetic carbonates. Geochimica et Cosmochimica Acta 1997, 61, (16), Okumura, M.; Kitano, Y., Coprecipitation of alkali metal ions with calcium carbonate. Geochimica et Cosmochimica Acta 1986, 50, (1), Zhong, S.; Mucci, A., Partitioning of rare earth elements (REEs) between calcite and sea solutions at 25 C and 1 atm, and high dissolved REE concentrations. Geochimica et Cosmochimica Acta 1995, 59, (3), Zhong, S.; Mucci, A., Calcite and aragonite precipitation from sea solutions of various salinities: Precipitation rates and overgrowth compositions. Chemical Geology 1989, 78, (3-4), Mucci, A.; Morse, J. W., The incorporation of Mg 2+ and Sr 2+ into calcite overgrowths: influences of growth rate and solution composition. Geochimica et Cosmochimica Acta 1983, 47, (2), Huang, Y.; Fairchild, I. J., Partitioning of Sr 2+ and Mg 2+ into calcite under karst-analogue experimental conditions. Geochimica et Cosmochimica Acta 2001, 65, (1), Gabitov, R. I.; Sadekov, A.; Lainweber, A., Crystal growth rate effect on Mg/Ca and Sr/Ca partitioning between calcite and fluid: An in situ approach. Chemical Geology 2014, 367, Gabitov, R. I.; Watson, E. B., Partitioning of strontium between calcite and fluid. Geochemistry, Geophysics, Geosystems 2006, 7, Q11004, doi: /2005gc Oomori, T.; Kaneshima, H.; Maezato, Y.; Kitano, Y., Distribution coefficient of Mg2+ ions between calcite and solution at C. Marine Chemistry 1987, 20, (4), Dromgoole, E. L.; Walter, L. M., Iron and manganese incorporation into calcite: Effects of growth kinetics, temperature and solution chemistry. Chemical Geology 1990, 81, Lorens, R. B., Sr, Cd, Mn and Co distribution coefficients in calcite as a function of calcite precipitation rate. Geochimica et Cosmochimica Acta 1981, 45, Lorens, R. B. A study of biological and physical controls on the trace metal content of calcite and aragonite. Ph.D. thesis. Univ. Rhode Island. USA, Temman, M.; Paquette, J.; Vali, H., Mn and Zn incorporation into calcite as a function of chloride aqueous concentration. Geochimica et Cosmochimica Acta 2000, 64, (14), Pingitore, N. E., Jr.; Eastman, M. P.; Sandidge, M.; Oden, K.; Freiha, B., The Coprecipitation of Manganese(II) with Calcite: an Experimental Study. Marine Chemistry 1988, 25, Nehrke, G.; Reichart, G. J.; Van Cappellen, P.; Meile, C.; Bijma, J., Dependence of calcite growth rate and Sr partitioning on solution stoichiometry: Non-Kossel crystal growth. Geochimica et Cosmochimica Acta 2007, 71, Tesoriero, A. J.; Pankow, J. F., Solid solution partitioning of Sr 2+, Ba 2+, and Cd 2+ to calcite. Geochimica et Cosmochimica Acta 1996, 60, (6), Pingitore, N. E., Jr.; Eastman, M. P., The coprecipitation of Sr 2+ with calcite at 25 C and 1 atm. Geochimica et Cosmochimica Acta 1986, 50, (10), Tang, J.; Köhler, S. J.; Dietzel, M., Sr 2+ /Ca 2+ and 44 Ca/ 40 Ca fractionation during inorganic calcite formation: I. Sr incorporation. Geochimica et Cosmochimica Acta 2008, 72, Qu, C.; Liu, G.; Zhao, Y., Experimental study on the fractionation of yttrium from holmium during the coprecipitation with calcium carbonates in sea solutions. Geochemical Journal 2009, 43, Pingitore, N. E.; Eastman, M. P., The experimental partitioning of Ba2+ into calcite. Chemical Geology 1984, 45, (1), S9

15 23. Terakado, Y.; Taniguchi, M., A new method for the study of trace element partitioning between calcium carbonate and aqueous solution: A test case for Sr and Ba incorporation into calcite. Geochical Journal 2006, 40, (2), Borg, I. Y.; Stone, R.; Levy, H. B.; Ramspott, L. D. Information pertinent to the migration of radionuclides in ground at the Nevada Test Site. Part 1. Review and analysis of existing information; United States, , Meece, D. E.; Benninger, L. K., The coprecipitation of Pu and other radionuclides with CaCO3. Geochimica et Cosmochimica Acta 1993, 57, (7), Kitano, Y.; Oomori, T., The coprecipitation of uranium with calcium carbonate. Journal of the Oceanographical Society of Japan 1971, 27, (1), S10