Comparing spatial and temporal changes in metal trends (Cr, Ni, Pb and Zn) on the Portuguese shelf since the 1970s.

Comparison between an archive dataset, collected during the 1970s (1974-1977), and samples taken during the PALEO1 cruise (2002) enabled evaluation of large-scale and long-term spatiotemporal changes in Al, Cr, Ni, Pb and Zn contents in bulk surface sediments in four areas of the Portuguese shelf. The so-called gradient method (GM) with normalisation to Al, a proxy for terrigenous clay content, was applied. The studied areas are distributed from north to south along the western margin, with the northernmost located off shore the Ave and Douro rivers, a central one located off shore the Lis River and a southern one located off shore the Mira River. One-way ANOVA and Kruskal-Wallis tests were used to identify differences among study areas and periods of sample collection. A comparison of metal contents in 2002 samples with the Portuguese classification scheme regulation for deposition of dredged materials in coastal areas indicates good environmental quality in terms of Cr, Ni, Pb and Zn levels. Nevertheless, the GM results suggest an increase in metal loadings relative to Al from the 1970s to the 2002 samples (except for Pb). The Algarve area on the southern shelf is characterised by having high number of sites with metal level on class 2. These high values have traditionally been explained by a substantial supply of natural metals from the Guadiana, Tinto and Odiel rivers that drain areas Iberian Pyrite Belt formations. This supply has probably been magnified by present and past mining activities. For quality evaluation of marine sediments, especially when using total metal contents, this study shows the importance of considering all possible sources of metal loading. The natural grain size and composition variability have also a crucial influence on the metal content, and the combined evaluation allows a more holistic perspective.

Spatial distribution and temporal trends of butyltin compounds (TBT, DBT & MBT) in short sediment cores of the SW Portuguese Shelf (western Iberian Margin, NE Atlantic).

Spatial patterns and temporal trends of the butyltin compounds tributyltin (TBT), dibutyltin (DBT), and monobutyltin (MBT) were investigated in a set of sediment samples collected along the SW Portuguese continental shelf. This region did not reach the Good Environmental Status (GES) in accordance with the Marine Strategy Framework Directive (MSFD) during a first evaluation carried out in 2012. Overall, MBT and DBT were the predominant organotin species detected, but high concentrations of TBT were found in and around disposal sites for dredge sludge derived from the dredging in navigation channels, harbours, and shipyard facilities of the Tagus and Sado estuaries. Although Portuguese regulations for monitoring sediment quality in relation to dredging activities consider only PAH, PCB and HCB, they also dictate that other organic contaminants such as butyltin compounds (BTs) should be monitored if suspicion of high values exists, but no action limits are defined for these (MAOTDR, 2007). Without action limits, the monitoring recommendation given in the regulations is not put into practice. Considering their toxicity, BT derivates should be integrated in the legislation, because they represent an environmental threat in the relocation of dredged material, especially when derived from harbour and shipyards areas. Based on this study, we recommend giving more attention to the amounts and impacts of BTs in sediments at dredged material disposal sites (DMDS) and their surroundings. Or even better, in order to be more efficient, monitoring should be done at the source of the dredged materials and not at the sink. In case it is not done, the monitoring of concentrations of TBT (and other BTs) in sediments and organisms, including imposex studies, at all Portuguese sites for disposal of dredged material receiving slightly to strongly contaminated dredged material must be developed.

Rare earth and trace elements in deep-sea sponges of the North Atlantic.

The available data on trace elements (TE) of deep-sea organisms is scarce and nonexistent for rare earth elements (REE). Hence, this study characterizes REE and TE in five porifera genera (Jaspis, Geodia, Hamacantha, Leiodermatium, Poliopogon) collected in deep-sea areas (between 481 and 2656 m) of the North Atlantic. Aluminium was the most common TE while lead was the less abundant. These sponges showed an increased accumulation of TE compared with other probably influenced by volcanic activity. Poliopogon amadou sampled at the deepest location presented the highest concentration of all REE. All studied species exhibited a Light REE enrichment in comparison to Heavy REE and showed a negative Ce anomaly with a less conspicuous Eu depletion. Besides the establishment of a baseline for future comparisons, this study provides the first record of REE in a sessile deep-sea marine invertebrate group.

Elemental composition of whole body soft tissues in bivalves from the Bijagós Archipelago, Guinea-Bissau.

Marine bivalves are bioindicators of coastal environmental pollution, integrating monitoring programs worldwide. Nonetheless, the choice of particular species as an indicator requires validation, achieved by understanding the differences in element concentrations among and within species. The present study compares the chemical composition of whole body soft tissues of four common bivalve species from the Bijagós Archipelago, a pristine region of West Africa. Significant differences were recorded in the concentrations of various elements among studied species, which likely arise from species-specific uptake and bioaccumulation processes. Overall, there was a segregation between a group including the bloody cockle Senilia senilis and oyster Crassostrea tulipa (with high Cd and Zn concentrations) versus the two other species, Austromacoma nymphalis (with low Cu and high Mn, Se, Hg, Pb concentrations) and Diplodonta spp. (with high values of Cu, Al, Fe, V, Cr, Hg, Pb). C. tulipa was sampled in two different substrates (rock beds and mangrove roots), and the two groups revealed different chemical profiles, with significantly higher concentrations of P, Si, Zn and Cr and lower Cu in specimens fixed in mangrove roots. These results strongly suggest the influence of small-scale environmental variability on the accumulation of particular elements. We found extremely high Cd concentrations in S. senilis (27.1 ± 7.53 µg g-1 DW) and identified C. tulipa as another high Cd-accumulating species (ca. 10 µg g-1 DW). Our results suggest a detoxifying mechanism linked with the presence of Se to reduce the potential toxic effects of Cd in these two species. Cadmium concentrations reported for some bivalve species in this area largely exceed the maximum values proposed by the European Union, emphasizing the need for a regular contamination assessment.

Influence of diagenetic processes and terrestrial/anthropogenic sources in the REE contents of the Cascais submarine canyon (Iberian western coast).

Temporal variations of rare earth elements (REE) and their fractionation patterns, major elements, Pb and Hg were determined in two multicores collected at 445 and 2100 m water depth (mwd) in the Cascais submarine canyon (CSC). The PAAS-normalized REE patterns suggest mixing of Tagus estuarine and marine sediments, marked by MREE (Nd-Dy series) enrichment and by positive Eu-anomaly, with marine sediments. The positive Eu/Eu* implies incorporation of detrital feldspar minerals derived from the estuary. Ce/Ce*, (La/Yb)PAAS and (Nd/Yb)PAAS show differences between the two cores. Core 252-35 from the shallower site is enriched in HREE (Ho-Lu series) over LREE (La-Pr series), a pattern also found in the Tagus estuary in the vicinity of an abandoned chemical complex, where the environment is affected by the legacy of massive-sulfide ores processing. There seems to be only limited down-canyon sediment transport to the deeper reaches where core 252-32 was collected. This deeper site shows Ce/Ce* peaks coinciding with low (La/Yb)PAAS values suggesting preferential diagenetic remobilization of LREE relative to HREE. Upcore Pb/Al and Hg/Corg trends observed in both cores indicate dispersion of the anthropogenic component from the estuary through the CSC, which is less obvious from the ∑REE/Al trends particularly in the deeper site. This may suggest the influence of diagenetic processes in the REE signal, associated with relatively low sediment accumulation rates.

Sources and distribution of yttrium and rare earth elements in surface sediments from Tagus estuary, Portugal.

The distribution and sources of yttrium and rare-earth elements (YREE) in surface sediments were studied on 78 samples collected in the Tagus estuary (SW Portugal, SW Europe). Yttrium and total REE contents ranged from 2.4 to 32mg·kg-1 and 18 to 210mg·kg-1, respectively, and exhibited significant correlations with sediment grain-size, Al, Fe, Mg and Mn, suggesting a preferential association to fine-grained material (e.g. aluminosilicates but also Al hydroxides and Fe oxyhydroxides). The PAAS (Post-Archean Australian Shale) normalized patterns display three distinct YREE fractionation pattern groups along the Tagus estuary: a first group, characterized by medium to coarse-grained material, a depleted and almost flat PAAS-normalized pattern, with a positive anomaly of Eu, representing one of the lithogenic components; a second group, characterized mainly by fine-grained sediment, with higher shale-normalized ratios and an enrichment of LREE relative to HREE, associated with waste water treatment plant (WWTP) outfalls, located in the northern margin; and, a third group, of fine-grained material, marked by a significant enrichment of Y, a depletion of Ce and an enrichment of HREE over LREE, located near an inactive chemical-industrial complex (e.g. pyrite roast plant, chemical and phosphorous fertilizer industries), in the southern margin. The data allow the quantification of the YREE contents and its spatial distribution in the surface sediments of the Tagus estuary, identifying the main potential sources and confirming the use of rare earth elements as tracers of anthropogenic activities in highly hydrodynamic estuaries.

Insights of Pb isotopic signature into the historical evolution and sources of Pb contamination in a sediment core of the southwestern Iberian Atlantic shelf.

Stable Pb isotopic ratios and concentrations of Al, Cu and Pb were measured in a 5m long sediment core (VC2B) retrieved at 96m water depth in the southwestern Iberian Atlantic shelf. Five phases during the last 9.5kyrs were identified, two of them (Roman Period and modern mining) marked by a decrease of 206Pb/207Pb ratios reflecting additional inputs of Pb derived from mining activities. The Roman Period was also characterized by high 208Pb/206Pb ratios suggesting the exploitation of the outcropping portion of the orebody intensely weathered when compared with the other formations later mined. The shift of 208Pb/206Pb ratios towards linearity took approximately 1.0kyrs, which may mirror the time of environmental recovery from the impact of Roman mining activities. The application of a mixing model allowed the quantification of the contribution associated with anthropogenic mining activities to the shelf sediments. The maximum values of Pb contamination occurred in the 20th century. This study gives direct evidence of Pb and Cu exploitation over the last 2000years. The stable Pb isotopic signatures point to legacy of mining activities that are still the prevailing metal source recorded in the southwestern Iberian Atlantic shelf sediments.

Reconstruction of organochlorine compound inputs in the Tagus Prodelta.

Twenty century time-resolved variability of riverine deposits of polychlorobiphenyls (PCBs), DDTs, hexachlorocyclohexanes (HCHs) and hexachlorobenzene (HCB) was studied in three (210)Pb dated sediment cores collected in a depositional shelf area adjacent to the Tagus estuary (the Tagus Prodelta). The geographic and temporal distribution patterns were consistent with discharge of these organochlorine compounds (OCs) in the area associated with the Tagus mouth. Their concentrations were not correlated with the sedimentary total organic carbon. The PCB down-core profiles were dominated by CB138 and CB153 (hexa-CBs) congeners followed by CB180 (hepta-CBs). Principal Component Analysis of the congener distributions of these compounds did not define temporal down-core trends. The ratios of DDT metabolites (p,p'-DDE/p,p'-DDT) were consistent with recent DDT inputs into the environment and/or earlier applications and long-term residence in soils/sediments until these were eroded and remobilized.

Footprint of roman and modern mining activities in a sediment core from the southwestern Iberian Atlantic shelf.

A 5-m long sediment core (VC2B), retrieved in the Southwestern Iberian Atlantic shelf, at 96m water depth, was used to assess major changes in climate and human activities during the last 9.7kyrs. Analytical measurements included sedimentological (mean grain size, and the contents of sand, silt and clay), geochemical (major, minor, trace and rare earth elements; REEs) and chronological ((210)Pb and (14)C) parameters. Two episodes of increment of fine-grained particles, occurring at 3050BCE and 1350CE, suggest the retreat of the coast line to the present level and the beginning of a wetter phase associated with the "Little Ice Age". The North American Shale Composite (NASC)-normalized REE-pattern detected in the shelf is similar to that found in the Guadiana estuarine sediments. The possibility of this estuary as a contributor to the sediment load deposited in the adjacent coastal zone was indicated. Trace elements were significantly correlated with Al until 1850CE, pointing that grain-size rules its distribution in sediments. The depth variation of As, Cu and Pb enrichment factors relative to background values shows two periods of intense human activity that can be mainly linked to mining: (i) across the Roman Period, marked by low enrichments; and (ii) starting on the second half of the 19th century until nowadays with significantly increased enrichments, especially of Pb and Cu. In addition to As, Cu and Pb, this period is also marked by high enrichments of Hg and Zn. Despite the decrease/closure of sulphide massive deposits mining exploitation (e.g., São Domingos, Las Herrerias) during the second half of the 20th century, results showed ongoing input of Pb, Cu, As, Hg and Zn to coastal sediments. Thus, the legacy of contamination by these elements, mainly from leaching of slags and tailings, and remobilization/reworking of contaminated estuarine sediments, is still recorded in marine sediments.

Temporal evolution of lead isotope ratios in sediments of the Central Portuguese Margin: a fingerprint of human activities.

Stable Pb isotope ratios ((206)Pb/(207)Pb, (208)Pb/(206)Pb), (210)Pb, Pb, Al, Ca, Fe, Mn and Si concentrations were measured in 7 sediment cores from the west coast of the Iberian Peninsula to assess the Pb contamination throughout the last 200 years. Independently of their locations, all cores are characterized by increasing Pb/Al rends not related to grain-size changes. Conversely, decreasing trends of (206)Pb/(207)Pb were found towards the present. This tendency suggest a change in Pb sources reflecting an increased proportion derived from anthropogenic activities. The highest anthropogenic Pb inventories for sediments younger than 1950s were found in the two shallowest cores of Cascais and Lisboa submarine canyons, reflecting the proximity of the Tagus estuary. Lead isotope signatures also help demonstrate that sediments contaminated with Pb are not constrained to estuarine-coastal areas and upper parts of submarine canyons, but are also to transferred to a lesser extent to deeper parts of the Portuguese Margin.

Evaluation of the contamination of platinum in estuarine and coastal sediments (Tagus Estuary and Prodelta, Portugal).

Platinum contamination in estuarine and coastal sediments has been evaluated in three cores collected from the Tagus Estuary and Prodelta shelf sediments. Elevated concentrations, up to 25-fold enrichment compared to background values, were found in the upper layers of the estuarine sediments. The degree of Pt enrichment in the estuarine sediments varied depending on the proximity to vehicular traffic sources, with a maximum concentration of 9.5 ng g(-1). A considerable decrease of Pt concentrations with depth indicated the absence of significant contamination before the introduction of catalytic converters in automobiles. Platinum distribution in the Tagus Prodelta shelf sediment core showed no surface enrichment; instead a sub-surface maximum at the base of the mixed layer suggested the possibility of post-depositional mobility, thereby blurring the traffic-borne contamination signature in coastal sediments.