Mapping the Microstructural Location of Salts and Metals in Sea Ice with X-Ray Micro-Fluorescence Spectroscopy

Abstract:

Sea ice forms a permeable boundary between the ocean and the atmosphere, mediating chemical, physical, and transport processes that can have large impacts on a changing climate. It is a complex media composed of ice, brine, air pockets, and salt precipitates whose fine microstructure is constantly evolving with time and temperature. To gain insight of the processes occurring within the sea ice, it is key to have an understanding of how the different phases interact. Using synchrotron x-ray micro-fluorescence (XRF) at Argonne National Laboratory's Advanced Photon Source (APS), we examined the microstructural location of different salts and metals in Antarctic sea ice. In particular, we sought to determine whether these elements are found solely in brine channels and at grain boundaries or exist ubiquitously throughout the crystal lattice of ice. Further, we also investigated the spatial distribution of each impurity to determine how microstructure may vary within the sea ice column.

Although it is well known that salts are expelled from the ice matrix during the freezing process and the bulk of impurities lies in brine inclusions and channels, providing quantitative and visual evidence with high resolution remains an ongoing process. XRF enables us to detect and map the precise microstructural and stratigraphic location of the constituent salts in sea ice. Cores were cut into 0.5 cm-thick slices every ten cm along the length of the core. At APS, a 2 mm x 2 mm region of each sample was scanned by an 18 kV X-ray beam and the resulting fluorescence signal detected using a silicon drift detector. By integrating the detected signal for the respective characteristic energy, we were able to obtain two-dimensional elemental maps with ten micron resolution for bromide, chloride, potassium, calcium, strontium, iron, copper, and zinc. Maps were compared to thin sections obtained under cross-polarizing lenses to identify particular features. We were able to show that salts exist exclusively at grain boundaries and in brine channels/layers. In addition, we were able to quantify the detected signal for bromide and found it to be up to thirty times the bulk concentration. By increasing our knowledge of the brine network microstructure, we yield a better understanding of the transport of heat, gases, and chemical species through sea ice.