Bromine soil/sediment enrichment in tidal salt marshes as a potential indicator of climate changes driven by solar activity: New insights from W coast Portuguese estuaries.

This paper aims at providing insight about bromine (Br) cycle in four Portuguese estuaries: Minho, Lima (in the NW coast) and Sado, Mira (in the SW coast). The focus is on their tidal marsh environments, quite distinct with regard to key biophysicochemical attributes. Regardless of the primary bromide (Br-) common natural source, i.e., seawater, the NW marshes present relatively higher surface soil/sediment Br concentrations than the ones from SW coast. This happens in close connection with organic matter (OM) content, and is controlled by their main climatic contexts. Yet, the anthropogenic impact on Br concentrations cannot be discarded. Regarding [Br] spatial patterns across the marshes, the results show a general increase from tidal flat toward high marsh. Maxima [Br] occur in the upper driftline zone, at transition from highest low marsh to high marsh, recognized as a privileged setting for OM accumulation. Based on the discovery of OM ubiquitous bromination in marine and transitional environments, it is assumed that this Br occurs mainly as organobromine. Analysis of two dated sediment cores indicates that, despite having the same age (AD ~1300), the Caminha salt marsh (Minho estuary) evidences higher Br enrichment than the Casa Branca salt marsh (Mira estuary). This is related to a greater Br storage ability, which is linked to OM build-up and rate dynamics under different climate scenarios. Both cores evidence a fairly similar temporal Br enrichment pattern, and may be interpreted in light of the sun-climate coupling. Thereby, most of the well-known Grand Solar Minima during the Little Ice Age appear to have left an imprint on these marshes, supported by higher [Br] in soils/sediments. Besides climate changes driven by solar activity and impacting marsh Br biogeodynamics, those Br enrichment peaks might also reflect inputs of enhanced volcanic activity covarying with Grand Solar Minima.

Bromine enrichment in marsh sediments as a marker of environmental changes driven by Grand Solar Minima and anthropogenic activity (Caminha, NW of Portugal).

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.

A 130 year record of pollution in the Suances estuary (southern Bay of Biscay): implications for environmental management.

Geochemical composition (Al, Zn, Pb, Cd, Cu, Ni, Cr and As) and foraminiferal assemblages in surface and core sediments were determined to assess the current situation and the recent environmental transformation of the Suances estuary (southern Bay of Biscay, Spain). Dating of the historical record has been achieved using isotopic analysis ((210)Pb, (137)Cs) and two benchmark events such as the beginning of the mineral exploitation in the Reocín Pb-Zn deposits and the evolution of the chlor-alkali industry (inputs of Hg). Concentrations of Zn, Pb and Cd in both surface and core samples are remarkably higher than background values, reflecting the existence of significant amounts of polluted materials. The dramatic environmental impact of this pollution is clearly recorded by the change of the foraminiferal assemblages that even reach an afaunal stage during recent decades. Application of two different sets of Sediment Quality Guidelines confirm that they exert potential risk to the environment, and therefore if dredged they should need specific management measures. The results provide a reference database to monitor future environmental changes in the Suances estuary, particularly as regards the contaminated sediment storage and the re-colonization by autochtonous meiofauna.

Geochemical and microfaunal proxies to assess environmental quality conditions during the recovery process of a heavily polluted estuary: the Bilbao estuary case (N. Spain).

This study explores the eventual environmental improvement of the Bilbao estuary (northern Spain), from 1997 to 2006, in order to assess current estuarine restoration being undertaken as part of a Revitalization Strategic Plan. The monitoring programme is based on spatial and temporal variation in the distributions of both benthic foraminiferal assemblages and heavy metals contained in surficial sediments from the polluted intertidal flats. The overall pattern shows a decreasing metal concentration; however, reversals to this trend are noticed in the middle estuary. From 2000 to 2003, a significant decrease in heavy metal concentration was observed which is most likely related to the implementation in 2001-2002 of the biological treatment at a central wastewater treatment plant. Although the metal concentration decreased by 85% for some elements, these values still remain considerably high. No significant change occurred between 2003 and 2006 in metal concentrations. During the monitoring period the estuary channel presented environmental conditions close to azoic in 3/4 of its watercourse. Only in the year 2006, the two lowermost estuarine samples exhibited an increase in microfaunal densities. These samples were dominated by pollution-resistant estuarine species. The fact that estuarine sediments quality is recovering very slowly seems to be caused mainly by the resuspension of accumulated contaminants in the sediments due to dredging and working activities in the estuary. Thus, local authorities should consider also the clean up of the pollutants stored in the sediments, not seeking only the achievement of the water quality standards, as these polluted sediments can act as source of contamination.

Environmental transformation of the Bilbao estuary, N. Spain: microfaunal and geochemical proxies in the recent sedimentary record.

The distribution and abundance of benthic foraminifera and a range of elements have been analysed in six long cores (up to 10 m long) from the Bilbao estuary, N. Spain, to document environmental transformation of this estuarine ecosystem and to determine sediment contamination levels. Three different environmental zones could be distinguished in the recent sedimentary record based on its microfaunal and geochemical contents. Initially, a pre-industrial zone containing very abundant and diverse foraminiferal assemblages together with baseline metal levels. Secondly, an older industrial zone exhibiting co-existence of abundant and diverse foraminiferal assemblages with high concentrations of metals. Finally, a younger industrial zone with extreme concentrations of metals and barren of indigenous foraminifera. This environmental transformation has been caused by the discharge of untreated domestic and industrial effluents during the last 150 years. The occurrence of foraminifera in the two industrial zones and along the estuary is not related to defined levels of metals, and this seems to confirm oxygen limitation as the key factor to explain complete estuarine defaunation during deposition of the younger industrial zone (period 1950-2000). Effectiveness of current regeneration schemes could be assessed using microfaunal and geochemical proxies as environmental quality indicators.