Description: This paper contains the results of an extensive isotopic study of United States Geological Survey GSD-1G and MPI-DING reference glasses. Thirteen different laboratories were involved using high-precision bulk (TIMS, MC-ICP-MS) and microanalytical (LA-MC-ICP-MS, LA-ICP-MS) techniques. Detailed studies were performed to demonstrate the large-scale and small-scale homogeneity of the reference glasses. Together with previously published isotopic data from ten other laboratories, preliminary reference and information values as well as their uncertainties at the 95% confidence level were determined for H, O, Li, B, Si, Ca, Sr, Nd, Hf, Pb, Th and U isotopes using the recommendations of the International Association of Geoanalysts for certification of reference materials. Our results indicate that GSD-1G and the MPI-DING glasses are suitable reference materials for microanalytical and bulk analytical purposes.

Description: The accurate interpretation of Si isotope signatures in natural systems requires knowledge of the equilibrium isotope fractionation between Si-bearing solids and the dominant Si-bearing aqueous species. Aqueous silicon speciation is dominated by silicic acid (H 4 SiO 4o ) in most natural aqueous fluids at pH 〈 8.5, but forms H 3 SiO 4⁻ , H 2 SiO 4²⁻ , and polymeric Si species in more alkaline fluids. In this study isotope exchange experiments were performed at bulk chemical equilibrium between amorphous silica (SiO 2 ∙0.32 H 2 O) and inorganic aqueous fluids at pH ranging from 5.8 to 9.9 at 25° and 75 °C with experiments running as long as 375 days. The three-isotope method was used to quantify the equilibrium Si isotope fractionation, Δ eq³⁰ Si, between amorphous silica and aqueous Si; at pH ∼ 6 this equilibrium fractionation factor was found to be 0.45 ± 0.2‰ at 25 °C, and 0.07 ± 0.6‰ at 75 °C. At more basic pH (〉9), equilibrium Si isotope fractionation factors between solid and aqueous solution are higher, at 1.63 ± 0.23‰ at 25 °C, and 1.06 ± 0.13‰ at 75 °C. Taking account of the distribution of the aqueous Si species, equilibrium Si isotope fractionation factors between H 3 SiO 4⁻ and H 4 SiO 4o of −2.34 ± 0.13‰ and −2.21 ± 0.05‰ at 25 and 75 °C, respectively, were determined. The distinct equilibrium isotope fractionation factors of H 3 SiO 4⁻ and H 4 SiO 4o , and its variation with temperature can be used to establish paleo-pH and temperature proxies. The application of the three-isotope method also provides insight into the rates of isotopic exchange. For the solid grain size used (∼20 nm), these rates match closely the measured bulk dissolution rates for amorphous silica for most of the isotope exchange process, suggesting the dominant and rate controlling isotope exchange mechanism in the experiments is detachment and reattachment of material at the amorphous silica surface.

Description: A commercial femtosecond laser system operating at its fundamental wavelength ({lambda} = 800 nm, near Infra-Red) was used to ablate both synthetic and natural quartz on polished and unpolished surfaces. Ablation rates and maximum depths were determined using two distinct optical setups: a 25 mm focal length Cassegrain reflecting objective, and a 50 mm focal length convergent coated lens. All samples were ablated with the same laser beam at E0 = 1 mJ, {tau} = 60 fs, f = 5 Hz and N = 10-8000 shots. The depth of ablation craters obtained with the lens shows a linear increase with shot number N up to N = 2000 shots. Then the depth increases much less with N and reaches a plateau above N = 3000 shots. Maximum depth was close to 1300 {micro}m for N = 3000 shots. Using the reflecting objective, ablation rate starts from 0.42 {micro}m/shot and decreases rapidly to 0.02 {micro}m/shot at a maximum depth of 350 {micro}m for N =1500 shots. Ablation thresholds (Fth) were calculated for 1 and 10 consecutive shots with energy increasing from E0 = 0.1-2 mJ/pulse. Threshold values varies from Fth=0.1 J.cm-2 (unpolished, 10 shots) to Fth = 2.9 J.cm-2 (polished, single shot). The energy penetration of IR-femtosecond laser pulses in quartz has been calculated at l = 271 nm. The low absorption of IR wavelengths in quartz affects the ablation efficiency in the first shots. The associated non-linear effects are visible on a crater FIB foil observed with TEM as progressive high-pressure photomechanical damage developing under the ablation pit. The present study emphasizes the potential of IR-femtosecond laser for ablation of highly transparent material, and provides reliable data for LA-ICP-MS applications in earth sciences.