This document discusses methods for estimating the marginal carbon dioxide (CO2) emissions rates associated with changes in electricity demand and the energy system. It finds that in Great Britain from 2002-2009, the marginal CO2 intensity of electricity was 0.69 kgCO2/kWh, higher than typical policy estimates. However, long-term CO2 reductions from interventions depend more on overall energy system changes modeled over decades than short-term operating margins. The key challenge is determining whether to use build or operating margins when assessing technologies' impacts on the energy system and CO2 emissions.