Bromine in Scapolite-Group Minerals and Sodalite: XRF Microprobe Analysis, Exchange Experiments, and Application to Skarn Deposits

Application of an X-ray fluorescence (XRF) microprobe for the analysis of single grains (80 to 1,000 m in diameter) of Cl-rich minerals for Br has been evaluated for fluorapatite, chlorapatite, scapolite-group minerals (marialite and meonite) and sodalite. A calibration curve based on the Br contents in four international reference materials has been confirmed by measurements on Br-bearing standard solutions and by agreement with the results of Cl-rich minerals from instrumental neutron-activation analyses. Absolute errors associated with individual XRF microprobe analyses (i.e., counting statistics alone) are less than 5%, and the calculated limit of detection in the analysis of single mineral grains is ~1 ppm Br. Matrix and grain-size effects are shown to be negligible. Experiments at 1 atmosphere and 800 to 1000°C yield the following distribution coefficients for Br–Cl exchanges between marialite or sodalite and hydrous NaCl–NaBr melts: KDmarialite–melt = 0.97 ± 0.08 and KDsodalite–melt = 0.9 ± 0.1. Therefore, the Cl/Br values in marialite and sodalite closely reflect the halogen proportions of their coexisting melts or fluids. The diffusivity of Br in sodalite follows an Arrhenius relation: DBr = 6.5 10–7 exp(–270 ± 10kJ/mol/RT) m2/s, over the temperature range from 800 to 1000°C. DBr in marialite is 1.7 ± 0.3 10–19 m2/s at 800°C. The Cl/Br weight ratios of marialite in the Tieshan Fe skarn deposit, China, cluster around 650 ± 40, supporting an origin involving hydrothermal brines from associated evaporites. Scapolite-group minerals in the exoskarns of the Nickel Plate Au skarn deposit, British Columbia, have Cl/Br from 560 to 570, higher than those (130 to 180) of their counterparts in the endoskarns and vuggy cavities. This variation is attributable to an increased