The nitrogen carrier in protoplanetary disks

The dominant reservoirs of elemental nitrogen in protoplanetary disks have not yet been observationally identified. Likely candidates are HCN, NH$_3$ and N$_2$. The relative abundances of these carriers determine the composition of planetesimals as a function of disk radius due to strong differences in their volatility. A significant sequestration of nitrogen in carriers less volatile than N$_2$ is likely required to deliver even small amounts of nitrogen to the Earth and potentially habitable exo-planets. While HCN has been detected in small amounts in inner disks ($<10$ au), so far only relatively insensitive upper limits on inner disk NH$_3$ have been obtained. We present new Gemini-TEXES high resolution spectroscopy of the 10.75 $\mu$m band of warm NH$_3$, and use 2-dimensional radiative transfer modeling to improve previous upper limits by an order of magnitude to $\rm [NH_3/H_{nuc}]<10^{-7}$ at 1 au. These NH$_3$ abundances are significantly lower than those typical for ices in circumstellar envelopes ($[{\rm NH_3/H_{nuc}}]\sim 3\times 10^{-6}$). We also consistently retrieve the inner disk HCN gas abundances using archival Spitzer spectra, and derive upper limits on the HCN ice abundance in protostellar envelopes using archival ground-based 4.7 $\mu$m spectroscopy ([HCN$_{\rm ice}$]/[H$_2$O$_{\rm ice}$]$<1.5-9$\%). We identify the NH$_3$/HCN ratio as an indicator of chemical evolution in the disk, and use this ratio to suggest that inner disk nitrogen is efficiently converted from NH$_3$ to N$_2$, significantly increasing the volatility of nitrogen in planet-forming regions.