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The Minho/Coura estuary, northern Portugal, has been studied for the influence of hydrochemical and geochemical parameters on living (Rose Bengal stained) foraminiferal assemblages. Our previous works showed a prevalence of agglutinated species in the inner estuary and tidal marsh and significant abundance of calcareous species only in the estuary mouth. The new results clarify syndepositional aspects of the calcareous species related to calcite dissolution, such as thin tests that frequently lack the carbonate layer and show typical destruction features. Sites from the estuary mouth, tidal marsh and river were sampled, under Spring and Autumn conditions, in order to describe physical-chemical features and to allow the geochemical modelling of the solution in which calcification occurs. In particular, the chemical equilibrium regarding calcite was evaluated from the saturation index (SI). Such modelling suggests strongly undersaturated conditions at the majority of the sampling sites, in both sampling periods. The water quality data revealed strong spatial and temporal variability, mainly in the tidal marsh environment, and also the existence of a stressed medium regarding calcite saturation state. The observed geochemical trends provide a plausible explanation for (1) the scarcity and distribution of living calcareous foraminifera in the Minho/Coura estuary and (2) the destruction features observed in the carbonate tests. [ABSTRACT FROM AUTHOR]

A sediment core collected in Caminha tidal marsh, NW Portugal, was used to assess bromine (Br) signal over the last ca. 1,700 years. The Br temporal variability reflects its close relationship with soil/sediment organic matter (OM) and also alterations in Br biogeochemical recycling in marsh environment. The highest Br enrichment in sediments was found during the Maunder Solar Minimum, a major solar event characterized by lower irradiance (TSI) and temperature, increased cloudiness and albedo. The obtained results suggest that those climate-induced changes weakened the natural mechanisms that promote Br biochemical transformations, driven by both living plants metabolism and plant litter degradation, with the ensuing generation of volatile methyl bromide (CH3Br). It seems that the prevailing climate conditions during the Maunder favoured the retention of more Br in marsh ecosystem, ultimately decreasing the biogenic Br emissions to the atmosphere. During the 20th century, the Br pattern in sediments appears to mirror likewise anthropogenic sources. The significant correlation (p<0.05) between Br/OM ratios and Pb contents in sediments after 1934 suggests a common source. This is most probably related with the rise, massive consumption and prohibition of leaded gasoline, where ethylene dibromide was added as lead scavenger to antiknock mixtures. More regionally, the concerted use of flame retardants on forest fire management, covering the 1980s through mid-1990s in the north of Portugal and Galicia, could be responsible for the observed increase of sediment Br (relatively to Pb) pool of this tidal marsh. Although man-made brominated compounds are being phased-out since the inception of the 1992 Montreal Protocol, the Caminha tidal marsh sedimentary record showed that Br levels only started to decline after 2002., (Copyright © 2014 Elsevier B.V. All rights reserved.)