Carbon and hydrogen isotopic composition of methane over the last 1000 years

New measurements of the carbon and hydrogen isotopic ratios of methane (delta C-13 of CH4 and delta D of CH4) over the last millennium are presented from the WAIS Divide, Antarctica, ice core (WDC05A), showing significant changes that likely were the result of human influences prior to the industrial revolution (at least as early as the 16th century of the common era (CE)). The delta C-13 of CH4 data corroborate the record from Law Dome, Antarctica, with high fidelity. The new delta D of CH4 data set covaries with the delta C-13 of CH4 record. Both delta C-13 of CH4 and delta D of CH4 were relatively stable and close to the present-day values from similar to 1000 to similar to 1500 CE. Both isotopic ratios decreased to minima around 1700 CE, remained low until the late 18th century, and then rose exponentially to present-day values. Our new delta D of CH4 data provide an additional independent constraint for evaluating possible CH4 source histories. We searched a broad range of source scenarios using a simple box model to identify histories consistent with the constraints of the CH4 concentration and isotope data from 990-1730 CE. Results typically show a decrease over time in the biomass-burning source (found in 85% of acceptable scenarios) and an increase in the agricultural source (found in 77% of acceptable scenarios), indicating preindustrial human influence on atmospheric methane as proposed in previous studies.