We explore the potential offered by large-mass Liquid Argon detectors for determination of the sign of Delta m_{31}^2, or the neutrino mass hierarchy, through interactions of atmospheric neutrinos. We give results for a 100 kT sized magnetized detector which provides separate sensitivity to \nu_\mu, \bar{\nu}\mu and, over a limited energy range, to \nu_e, \bar{\nu}e.We also discuss the sensitivity for the unmagnetized version of such a detector. After including the effect of smearing in neutrino energy and direction and incorporating the relevant statistical,theoretical and systematic errors, we perform a binned \chi^2 analysis of simulated data. The \chi^2 is marginalized over the presently allowed ranges of neutrino parameters and determined as a function of \theta{13}. We find that such a detector offers superior capabilities for hierarchy resolution, allowing a > 4\sigma determination for a 100 kT detector over a 10 year running period for values of \sin^2 2\theta{13} \ge 0.05. For an unmagnetized detector, a 2.5\sigma hierarchy sensitivity is possible for \sin^2 2\theta_{13} = 0.04.

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