A headspace sampling system monitors materials in wastewater. The headspace sampling system comprises a sample receptacle that can contain a wastewater sample; a sparger chamber vapor column; a sample receptacle cover assembly that connects the sparger chamber vapor column to the sample receptacle; a sparger tube; at least one sensing device; and at least one analytic device. The sparger tube and the sample receptacle define a headspace. The sparger chamber vapor column is in communication with the sample receptacle and is closed by a sparger chamber vapor column cover at a second end that is opposed to the sample receptacle. The sparger tube extends into the sample receptacle and the wastewater sample in the sample receptacle. The sparger tube is connected to a source of inert gas at a first end opposed to the sample receptacle and comprises a dispersion device at an end opposed to the first end. The sensing device is disposed in the headspace sampling system in the headspace. The analytic device in communication with the least one sensing device. Inert gas can flow through the sparger tube into the wastewater sample to separate materials from the wastewater, the sparged materials entering the headspace of the headspace sampling system. The sparged materials are sensed by the sensing device thus providing material signal characteristics, which can be analyzed by the analytic device to determine characteristics of the material from the material signal characteristics and provide information about the characteristics of the material.