The oxidation of high concentrations of phenol and 2,4-dinitrophenol (DNP) was investigated in a pilot-scale supercritical water oxidation (SCWO) system. Treatment for approximately 40 s at a pressure of 25 MPa, temperatures of 666-778 K and oxygen excess of 0-34%, resulted in phenol destruction from 94 to 99.98%, consistent with extrapolations of some global rate laws proposed in the literature. Destruction of total organic carbon (TOC) varied from 75 to 99.77%. Two different solutions that contained DNP were studied following the phenol experiments. The first solution contains 2.4 wt.% of 2,4-DNP with 2.1 wt.% of ammonium sulphate. Treatment at under 43 s at 25 MPa, 780 K with a large oxygen excess, resulted in destruction efficiencies of over 99.9996% for DNP and 99.92% for TOC. Mono-nitrophenols were detected as intermediates, but not in the final effluent, where residuals of ammonium bicarbonate and sulphates were detected. This solution was extremely corrosive to the Alloy 625 preheaters at temperatures of approximately 370 degreesC. The second solution contained 2.26 wt.% of 2,4-DNP, with ammonia but no sulphates and was treated at 24.5 MPa, 742-813 K and oxygen concentrations ranging from sub-stoichiometric to 67% excess. Destruction efficiencies for 2,4-dinitrophenol were over 99.9996% in all cases. TOC destruction efficiencies ranged from 98.98 to 99.98%, while ammonia destruction ranged from 15 to 50%. Picric acid and mono-nitrophenols were detected as intermediates, but not in the liquid effluent. No CO or NOx was present in the effluent gas samples, except in cases with less than stoichiometric oxygen. (C) 2003 Elsevier B.V. All rights reserved.