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The chemical speciation analysis of chromium in one of the most important South American Estuary was performed for the first time. Samples were collected in Patos Lagoon Estuary (Brazil) and were analysed by adsorptive cathodic stripping voltammetry, with the following analytical figures of merit: limit of detection, 0.1 nmol L(-1); precision RSD = 3%, n = 7; linearity, from limit of quantitation up to 20 nmol L(-1); and accuracy of 99.8%, expressed as recovery. No labile chromium forms were identified in samples, beside industries and a city were near the study area. It is pointed out a reverse correlation between total and non-active chromium and salinity, which could be explained by biogeochemical processes.

Summary We investigated the distribution of naturally occurring geochemical tracers ( 222 Rn, 223 Ra, 224 Ra, 226 Ra, CH 4 , δ 18 O, and δ 2 H) in the water column and adjacent groundwater of Mangueira Lagoon as proxies of groundwater discharge. Mangueira Lagoon is a large (90 km long), shallow (∼4–5 m deep), fresh, and non-tidal coastal lagoon in southern Brazil surrounded by extensively irrigated rice plantations and numerous irrigation canals. We hypothesized that the annual, intense irrigation for rice agriculture creates extreme conditions that seasonally change groundwater discharge patterns in the adjacent lagoon. We further supposed that dredging of irrigation canals alters groundwater fluxes. While the activities of 222 Rn in shallow groundwater were 2–3 orders of magnitude higher than in surface water, CH 4 and radium isotopes were only ∼1 order of magnitude higher. Therefore, 222 Rn appears to be the preferred groundwater tracer in this system. Radon concentrations and conductivities were dramatically higher near the pump house of rice irrigation canals, consistent with a groundwater source. Modeling of radon inventories accounting for total inputs (groundwater advection, diffusion from sediments, and decay of 226 Ra) and losses (atmospheric evasion, horizontal mixing and decay) indicated that groundwater advection rates in the irrigation canals (∼25 cm/d) are over 2 orders of magnitude higher than along the shoreline (∼0.1 cm/d). Nearly 75% of the total area of the canals is found in the southern half of the lagoon, where groundwater inputs seem to be higher as also indicated by methane and stable isotope trends. In spite of the relatively small area of the canals, we estimate that they contribute nearly 70% of the total (∼57,000 m 3 /d) groundwater input into the entire Mangueira Lagoon. We suggest that the dredging of these canals cut through aquitards which previously restricted upward advection from the underlying permeable strata. The irrigation channels may therefore represent an important but previously overlooked source of nutrients and other dissolved chemicals derived from agricultural practices into the lagoon.

This study assesses the importance of groundwater discharge to dissolved nutrient levels in Mangueira Lagoon. A transect of an irrigation canal in the margin of Lagoon demonstrated a strong geochemical gradient due to high groundwater inputs in this area. Using 222Rn as a quantitative groundwater tracer, we observed that the flux of dissolved inorganic nitrogen (DIN), silicate and phosphate (1178 and 1977; 26190 and 35652; 167 and 188 mol d-1 for winter and summer, respectively) can continually supply/ sustain primary production. The irrigation canals act as an artificial underground tributary and represent a new source of nutrients to coastal lagoons.