Abstract: Methods and related devices are provided for probing a surface by application of a hyperpolarized noble gas having a nuclear electric quadrupole moment to the surface. In an embodiment, the hyperpolarized noble gas is substantially free of alkali metal vapor, such as rubidium vapor used to hyperpolarize the noble gas. Noble gas interaction with the surface of interest is detected by measuring quadrupolar-driven events such as T1, T2 relaxation or coherent processes by nuclear magnetic resonance spectroscopy or by magnetic resonance imaging, for example. The method is capable of probing a variety of surfaces that are difficult to analyze by conventional methods, including biological or non-biological surfaces, to obtain detailed and reliable information related to surface chemical composition.