The results of a comparison between chemical water quality determinants and river water fluorescence on the River Tyne, NE England, demonstrate that tryptophan-like fluorescence intensity shows statistically significant relationships between nitrate, phosphate, ammonia, biochemical oxygen demand (BOD) and dissolved oxygen. Tryptophan-like fluorescence intensity at the 280 nm excitation/350 nm emission wavelength fluorescence centre correlates with both phosphate (r = 0·80) and nitrate (r = 0·87), whereas tryptophan-like fluorescence intensity at the 220 nm excitation/350 nm emission wavelength centre correlates with BOD (r = 0·85), ammonia (r = 0·70) and dissolved oxygen (r = −0·65). The strongest correlations are between tryptophan-like fluorescence intensity and nitrate and phosphate, which in the Tyne catchment derive predominantly from point and diffuse source sewage inputs. The correlation between BOD and the tryptophan-like fluorescence intensity suggests that this fluorescence centre is related to the bioavailable or labile dissolved organic matter pool. The weakest correlations are observed between tryptophan-like fluorescence intensity and ammonia concentration and dissolved oxygen. The weaker correlation with ammonia is due to removal of the ammonia signal by wastewater treatment, and that with dissolved oxygen due to the natural aeration of the river such that this is not a good indicator of water quality. The observed correlations only hold true when treated sewage, sewerage overflows or cross connections, or agricultural organic pollutants dominate the water quality—this is not true for two sites where airport deicer (propylene glycol, which is non-fluorescent) or landfill leachate (which contains high concentrations of humic and fulvic-like fluorescent DOM) dominate the dissolved organic matter in the river. Mean annual tryptophan-like fluorescence intensity agrees well with the General Water Quality Assessment as determined by the England and Wales environmental regulators, the Environment Agency. Copyright © 2004 John Wiley & Sons, Ltd.