<p>By classical Fatou type theorems in various setups, it is well-known that positive harmonic functions have non-tangential limit at almost every point on the boundary. In this paper, in the setting of non-positively curved Harmonic manifolds of purely exponential volume growth, we are interested in the size of the exceptional sets of points on the boundary at infinity, where a suitable function blows up faster than a prescribed growth rate, along radial geodesic rays. For Poisson integrals of complex measures, we obtain a sharp bound on the Hausdorff dimension of the exceptional sets, in terms of the mean curvature of horospheres and the parameter of the growth rate. In the case of the Green potentials, we obtain similar upper bounds and also construct Green potentials that blow up faster than a prescribed rate on lower Hausdorff dimensional realizable sets. So we get a gap in the corresponding Hausdorff dimensions due to the assumption of variable pinched non-positive sectional curvature. We also obtain a Riesz decomposition theorem for subharmonic functions. Combining the above results we get our main result concerning Hausdorff dimensions of the exceptional sets of positive superharmonic functions.</p>