Photon counting (PhC) is an effective detection technology for underwater optical wireless communication (OWC) systems. The presence of signal-dependent Poisson shot noise and asynchronous multi-user interference (MUI) complicates the processing of received data signals, hindering the effective signal detection of PhC OWC systems. This paper proposes a novel iterative signal detection method in grant-free, multi-user, underwater PhC OWC systems with signal-dependent Poisson shot noise. We first introduce a new synchronization algorithm with a unique frame structure design. The algorithm performs active user identification and transmission delay estimation. Specifically, the estimation is performed first on a user group basis and then at the individual user level with reduced complexity and latency.We also develop a nonlinear iterative multi-user detection (MUD) algorithm that utilizes a detection window for each user to identify interfering symbols and estimate MUI on a slot-by-slot basis, followed by maximuma-posterioriprobability detection of user signals. Simulations demonstrate that our scheme achieves bit error rates comparable to scenarios with transmission delays known and signal detection perfectly synchronized.