Employees often struggle to identify ``who knows what,'' leading to organizational productivity losses. We investigate whether Large Language Models (LLMs) can infer individual domain knowledge directly from long-term Slack logs. Analyzing 27,188 messages from 43 users, we evaluated seven models (including Gemini, Claude, and GPT families) by comparing their zero-shot estimates against self-reported skill ratings from 27 participants. Gemini 2.5 Flash achieved the lowest error (MAE 21.13%), while GPT models showed significantly larger discrepancies. Notably, estimation accuracy depended only weakly on message volume, indicating that more text alone does not guarantee better inference. These findings demonstrate the feasibility and current limits of automated expertise mapping, highlighting the need for privacy-preserving deployments and richer, structure-aware representations of human knowledge.