1. A replicated natural experiment was used to assess the influence of pH and low alkalinity on abundance and richness of invertebrate families in streams draining catchments that receive acid deposition. Individual streams were used as the unit of replication, allowing conclusions to refer to a class of streams rather than to particular streams.

2. We also controlled for several factors other than pH and alkalinity, including flow and temperature, that are recognized as determinants of invertebrate distribution. Samples were from indigenous rocks, standardized for size, surface area, and geology.

3. Repeated measures analyses of variance (ANOVA) revealed that invertebrate abundance and richness were significantly lower at pH 5.8 than at pH 7.1 for the total community. Thirty per cent of the forty‐seven families exhibited significantly lower abundance at pH 5.8; thirteen families were absent at pH 5.8. Differences were greatest for Ephemeroptera: species richness was significantly lower at pH 5.8, and 71% of the twenty‐four species were either absent (seven) or found in reduced abundance (ten) in the acidic streams.

4. Stream alkalinity is projected to continue to decrease with continued acid deposition in the Shenandoah National Park. Concurrent decreases in pH may lead to the absence or continued numerical decline of certain Ephemeroptera species in streams that acidify to less than pH 6.0 and/or 50μEql⁻¹ alkalinity.