Groundwater contaminated with a mixture of 14 volatile chlorinated hydrocarbons (VCHs) discharges to an estuarine embayment in Sydney, Australia. A screening-level hazard assessment identified a potential risk to aquatic organisms from surface water contaminated by the groundwater. Direct toxicity assessment of the groundwater was undertaken on 5 indigenous marine species to assess toxicity and derive a site-specific guideline. The testing included acute tests, subchronic tests on early life stages, and a chronic test. Test organisms included a microalga (Nitzschia closterium), an amphipod (Allorchestes compressa), a polychaete worm (Diopatra dentata), and sea urchin (Heliocidaris tuberculata) and oyster larvae (Saccostrea commercialis). Toxicity testing was undertaken in sealed containers to prevent loss of VCHs, and concentrations of VCHs were measured to accurately assess exposure concentrations. No observed effect concentration (NOEC) values varied from 1.56% dilution (1.11 mg total VCHs) to 50% dilution (45.5 mg total VCHs). EC50 values varied from 4.8% dilution (3.77 mg total VCHs) to more than 50% dilution (45.5 mg total VCHs). NOEC data were used to derive species sensitivity distributions (SSDs) and a site-specific guideline. SSDs were derived from Burr type III (including the Pareto) and log-normal distributions. The log-normal distribution represented the best fit, and because the Pareto distribution is a finite threshold model more suited to toxicants with a threshold mode of action, the log-normal SSD and the associated 95% trigger value (TV) of 830 μg/L of total VCHs, was adopted as the site-specific TV for the groundwater.