SUMMARY 1. Water from acid (pH 4.3–5.7), brown water streams was low in alkalinity (0–2.3 g m−3 CaCO3) and conductivity (2.5–4.1 mS m−1) but contained relatively high concentrations of dissolved organic carbon (6.6–16.3 gm−3). In contrast, alkaline (pH 6.6–8.0), clearwater streams had high CaCO3 (12.6–57.6 g m−3) and conductivity (3.7–22.3 mS m−1) but low dissolved organic carbon concentrations (0.3–4.7 g m−3).2. Total reactive aluminium (Al) concentrations were high in acid streams (123–363 mg m−3) but never exceeded 84 mg m−3 in alkaline streams. Acid‐soluble and organic monomeric Al were the major Al species in the acid streams (31–168 and 84–178mg m−3, respectively). Concentrations of toxic inorganic monomeric Al were low in all streams (<50mg m−3).3. Sixty‐four invertebrate taxa were collected from the alkaline streams compared to forty‐seven from the acid sites. Numbers of taxa in specific insect orders were similar at all sites, however. Benthic faunas at most sites were dominated by the mayfly Deleatidium sp. and chironomids.4. Overall, mean densities of benthic invertebrates were 2.4–4.8 times higher in alkaline streams than acid streams. No seasonal patterns of abundance were evident at any site.5. Temporal variability of invertebrate densities was correlated with stream channel stability such that fluctuations in densities declined as stability increased.6. Sources of dissolved organic carbon and aluminium in acid, brown water streams are discussed. We suggest that changes in the food supply available in acid streams account for the depauperate faunas found there.