This contribution presents a new perspective on water chemistry and its relation to tidal hydrology in marsh-dominated estuaries. Results are derived from both field and modeling experiments. A heuristic model based on a tidally-averaged advection-dispersion equation is used in conjunction with source-sink terms (for benthic, marsh surface, and open-water exchanges) to make predictions of nutrient concentrations in the water column. Spring-neap tidal contrasts are associated with significant changes in water-column chemistry for a variety of nutrients sampled during the growing season in the Parker River estuary (Massachusetts). For ammonium, phosphate, nitrate plus nitrite, total dissolved N, and total dissolved P, concentrations are significantly lower during spring tides (marshes flooded) than during neap tides (marshes unflooded). Model results indicate that physical changes and open-water processing are insufficient to produce the observed effect, and that explicit biogeochemical processing on marsh surfaces is required. Field observations of changes in nutrient to nutrient ratios with the onset of marsh inundation also support this conclusion. As tides progress from the neap to spring condition, a ''spectrum'' of trajectories emerges in salinity-nutrient plots developed from both observational datasets and model output. Care must therefore be exercised in designing sampling programs for water chemistry in marsh-dominated ecosystems and in interpreting the resulting mixing diagrams.
