Lazaro Luiz Mattos Laut

Assessment of the health quality of Ria de Aveiro (Portugal): Heavy metals and benthic foraminifera

This work analyses the distribution of heavy metals in the sediments of Ria de Aveiro (Portugal) assessed by total digestion and sequential chemical extraction of the sediments. The influence of environmental parameters on the living benthic foraminiferal assemblages was studied. The most polluted parts in the Ria de Aveiro are areas where the residence time is high and cohesive sediments are deposited. Organic matter, which is an excellent scavenger for a number of metals, is in general more abundant in the finer deposits of this lagoon, which act as sinks of anthropogenic pollutants. This condition is observed in Aveiro canals and Murtosa channel where sediments with the highest concentrations of Zn, Pb, Cu, and Cr are found. The sediments of Murtosa channel are also enriched in As, Co and Hg. In Aveiro canals the enrichment of heavy metals is mostly related to the past industrial production at their margins (ceramic and metallurgy), whereas in Murtosa channel with effluent discharges of the Chemical Complex of Estarreja. Foraminiferal density and diversity reach higher values near the lagoon mouth under higher marine influence and decline in general under very low-oxygen conditions. Some species seems to be indifferent to the increasing of TOC (e.g. Haynesina germanica and Ammonia tepida) and some have an opportunistic behaviour in areas with very depressed levels of oxygen (e.g. A. tepida and Quinqueloculina seminulum) whereas other species can better tolerate sulphide/reducing conditions (e.g. H. germanica, Bolivina ordinaria, Buliminella elegantissima, Bulimina elongata/gibba and Nonionella stella) a widespread condition in this lagoon. Foraminiferal density and some species are negatively correlated with concentrations of heavy metals. A most sensitive group of species to higher concentrations of heavy metals is identified (such as B. ordinaria, B. pseudoplicata and B. elongata/gibba) and another one of more tolerant species (such as H. germanica A. tepida and Q. seminulum). Foraminifera are more tolerate higher available concentrations (AC) of Zn in any phase than higher AC of Cu adsorbed do clay minerals (F1) and associated with Fe and Mn oxides (F2) and of Pb in F2; the phase F2, probably the most mobile phase, and even phase F1 seems to be more toxic than the increasing of metals in organic matter (F3).

Response of Benthic Foraminifera to Organic Matter Quantity and Quality and Bioavailable Concentrations of Metals in Aveiro Lagoon (Portugal)

This work analyses the distribution of living benthic foraminiferal assemblages of surface sediments in different intertidal areas of Ria de Aveiro (Portugal), a polihaline and anthropized coastal lagoon. The relationships among foraminiferal assemblages in association with environmental parameters (temperature, salinity, Eh and pH), grain size, the quantity and quality of organic matter (enrichment in carbohydrates, proteins and lipids), pollution caused by metals, and mineralogical data are studied in an attempt to identify indicators of adaptability to environmental stress. In particular, concentrations of selected metals in the surficial sediment are investigated to assess environmental pollution levels that are further synthetically parameterised by the Pollution Load Index (PLI). The PLI variations allowed the identification of five main polluted areas. Concentrations of metals were also analysed in three extracted phases to evaluate their possible mobility, bioavailability and toxicity in the surficial sediment. Polluted sediment in the form of both organic matter and metals can be found in the most confined zones. Whereas enrichment in organic matter and related biopolymers causes an increase in foraminifera density, pollution by metals leads to a decline in foraminiferal abundance and diversity in those zones. The first situation may be justified by the existence of opportunistic species (with high reproduction rate) that can live in low oxic conditions. The second is explained by the sensitivity of some species to pressure caused by metals. The quality of the organic matter found in these places and the option of a different food source should also explain the tolerance of several species to pollution caused by metals, despite their low reproductive rate in the most polluted areas. In this study, species that are sensitive and tolerant to organic matter and metal enrichment are identified, as is the differential sensitivity/tolerance of some species to metals enrichment.

Environmental Quality Assessment of Bizerte Lagoon (Tunisia) Using Living Foraminifera Assemblages and a Multiproxy Approach

This study investigated the environmental quality of the Bizerte Lagoon (Tunisia) through an integrated approach that combined environmental, biogeochemical, and living benthic foraminiferal analyses. Specifically, we analyzed the physicochemical parameters of the water and sediment. The textural, mineralogical, and geochemical characteristics of the sediment, including total organic carbon, total nitrogen, simultaneously extracted metals (SEM), acid volatile sulfides (AVS), chlorophyll a, CaCO3, and changes in bacterial populations and carbon isotopes were measured. The SEM/AVS values indicated the presence of relatively high concentrations of toxic metals in only some areas. Foraminiferal assemblages were dominated by species such as A. parkinsoniana (20–91%), Bolivina striatula (<40%), Hopkinsina atlantica (<17%), and Bolivina ordinaria (<15%) that cannot be considered typical of impacted coastal lagoons both in Mediterranean and northeast Atlantic regions. The results of this work suggest that Bizerte Lagoon is a unique setting. This lagoon is populated by typical marine species that invaded this ecosystem, attracted not only by the prevailing favorable environmental conditions but also by the abundance and quality of food. The results indicate that the metal pollution found in some areas have a negative impact on the assemblages of foraminifera. At present, however, this negative impact is not highly alarming.

Foraminiferal biotopes and their distribution control in Ria de Aveiro (Portugal): a multiproxy approach

Ria de Aveiro, which is located in the centre of Portugal (40° 38′ N, 8° 45′ W), is a well-mixed and complex coastal lagoon that is separated from the sea by a sandy barrier and connects with the Atlantic through an artificial inlet. Tidal currents are the main factor controlling the lagoon’s hydrodynamics and, to a great extent, the sedimentary dynamic. The inner lagoonal zones receive input from several rivers and experience the pressure caused by the accumulation of organic matter and pollutants (namely, trace metals) from diverse anthropic activities. This paper is the first piece of work aiming to recognize, characterize and explain the main benthic foraminiferal biotopes in Ria de Aveiro. To provide a broad overview of this kind of setting, our results are compared to those of previous published studies conducted in similar transitional environments. The research is based on an investigation of 225 sites spread throughout this ecosystem. Utilizing a statistical approach, this study analyses the details of dead benthic foraminiferal assemblages composed of 260 taxa, the texture and composition (mineralogical and geochemical) of the sediment and physicochemical data. On the basis of the results of R-mode and Q-mode cluster analyses, several different biotopes can be defined as marsh biotope/near-marsh biotope; marginal urban/marginal urban mixing biotope; inner-outer lagoon biotope or enclosed lagoon; outer lagoon biotope, mixed sub-biotope; and outer lagoon, marine sub-biotope. These biotopes are related to foraminifera assemblages and substrate type and are influenced by local currents, water depth, chemical and physicochemical conditions, river or oceanic proximity, and anthropogenic impact, as evidenced by the mapping of the six factor loadings of the principal component analysis conducted herein. Based on a similar methodology of analysis as that applied in previous studies in the Lagoon of Venice, comparable biotypes were identified in Lagoon of Aveiro.

Early diagenesis and clay mineral adsorption as driving factors of metal pollution in sediments: the case of Aveiro Lagoon (Portugal)

This work aims to define the factors driving the accumulation of metals in the sediment of the lagoon of Aveiro (Portugal). The role of initial diagenetic processes in controlling trace metal retention in surface sediment is traced by mineralogy, magnetic susceptibility and geochemical analyses. Although several studies have focused on the metal distribution in this polihaline and anthropized coastal lagoon, most of them have been solely focused on the total metal concentrations. This study instead represents the first attempt to evaluate in a vast area of the Aveiro Lagoon the role of biogeochemical processes in metal availability and distribution in three extracted phases: exchangeable cations adsorbed by clay and elements co-precipitated with carbonates (S1), organic matter (S2) and amorphous Mn hydroxides (S3). According to the sediment guideline values, the sediment is polluted by, for instance, As and Hg in the inner area of the Murtosa Channel, Pb in the Espinheiro Channel, Aveiro City canals and Aveiro Harbour, and Zn in the northern area of the Ovar Channel. These sites are located near the source areas of pollutants and have the highest total available concentrations in each extracted phase. The total available concentrations of all toxic metals are however associated, firstly, with the production of amorphous Mn hydroxides in most of the areas and, secondly, with adsorption by organic compounds. The interplay of the different processes implies that not all of the sites near pollution sources have polluted surface sediment. The accumulation of metals depends on not only the pollution source but also the changing in the redox state of the sediments that may cause alterations in the sediment retention or releasing of redox-sensitive metals. Results of this work suggest that the biogeochemical processes may play a significant role in the increase of the pollutants in the sediment of the Aveiro Lagoon.

Biochemical Composition and Foraminiferal Content of Sediments for Determining Bottom Sector Environments in Guanabara Bay (Rio de Janeiro, Brazil)

ABSTRACT Clemente, I.M.M.M.; da Silva, F.S.; Laut, L.L.M.; Frontalini, F.; da Costa, V.L.; da Conceição Rodrigues, M.A.; Pereira, E.; Bergamaschi, S.; Filho, J.G.M., and Martins, M.V.A., 2015. Biochemical composition and foraminiferal content of sediments for determining bottom sector environments in Guanabara Bay (Rio de Janeiro, Brazil). Three cities in Brazil—Rio de Janeiro, Niterói, and São Gonçalo—with an estimated total population of 11 million people, are located in the surroundings of Guanabara Bay (RJ-Brazil), making it a highly contaminated coastal system. Because of its importance, Guanabara Bay has been one of the most studied coastal environments in Brazil. Despite that, this study represents the first investigation, to our knowledge, to couple benthic foraminifera with the quantity and quality of organic matter in the area. The spatial distribution of water salinity and the surface sediment reduction potential, grain size, total organic carbon, sulfur, bacterial organic carbon, biopolymers such as carbohydrates, proteins, lipids, bacterial enzyme esterase, and total foraminiferal assemblages were studied at 30 stations in Guanabara Bay. Based on these data, six bottom environments—industrial, marginal urban, marginal urban/industrial mixing, eutrophic, transitional, and outer— were identified and described.

Speciation of rare earth elements in surface sediments of Lagoon of Aveiro (N Portugal)

ABSTRACT Martins, V.A., Dias, J.A., Laut, L.M., Sobrinho, F., Santos, J.F., Rodrigues, M. A., Frontalini, F., Miranda, P., Terroso, D., Fernández-Fernández, S., Bernardes, C., Figueira, R., Sousa, S., Amaral, P., Mahiques, M., Bernabeu, A., Rey, D., Rubio, B., and Rocha, F., 2013. Speciation of rare earth elements in surface sediments of Lagoon of Aveiro (N Portugal). The goal of this work is to determine the distribution of the rare earth elements in the surface sediments in the Ria de Aveiro (N Portugal) coastal lagoon. Concentrations of REE (La, Ce, Nd, Sm) and related elements (Th, Y and Sc) were evaluated by total digestion of sediments in the fine fraction of 33 grab-samples of surface sediments. The same method was followed for Al, Ca, S and Zr, related to terrigenous sources, but also, in the cases of Ca and S, to biogenic and quimiogenic processes. Concentrations of REE and related elements were additionally assessed by a three-step sequential chemical extraction (E1-3) procedure coupled with ICP MS determination. The geochemical results were processed by statistical analysis combining textural and mineralogical data (XRD techniques). The results show that mobile La, Ce, Nd, Sm and Y are mostly adsorbed by amorphous Mn hydroxide (E3), secondly associate with organic matter (E2) and only in a very small extent are adsorbed on clay mineral structural sheets or associated with carbonates (E1). Thorium and Sc are almost exclusively linked with E2. Ytrium shows a very high percentage of availability, whilst Ce, La, Sc and Th are by far less mobile. Results of cluster analysis reveals that sediments are enriched in: i) quartz, feldspars and anhydrite in the most hydrodynamic areas with good connection with the ocean, where tidal currents are stronger and water is salty and well-oxygenated; ii) mud, TOC, phyllosilicates, siderite, pyrite and S in low hydrodynamic areas. In these areas, pyrite and siderite can result from reducing bacterial activity in subsurface sediments. Early diagenetic changes in the sediments would also influence the elements adsorption to clay minerals and their co-precipitation with carbonates (E1). The highest values of REE, in E1, occur in distal locations in relation to the mouths of rivers and streams. The retention of the elements in this phase may occur mainly in the lagoon, depending on the availability of carbonates and clay minerals and their assemblages composition. Concentrations of REE and related elements adsorbed by organic matter (E2) and by amorphous Mn hydroxide (E3) tend to rise near the rivers mouths and may be related to geochemical processes that take place upstream in the course of the rivers before the entry of sediments into the lagoon. Elemental concentrations retained in the structure of mineral phases (R), also tend to reach high values near the rivers mouths but in low hydrodynamic areas. There is some fractionation between Th and the light REE which is more evident in the Murtosa channel that is fed mainly by the Antuã river.

The ITRAX core scanner, a useful tool to distinguish anthropic vs. climatic influences in lagoon of Aveiro (N Portugal)

ABSTRACT Martins, V. A., Dias, J. A., Bernardes, C., Rubio, B., Bernabeu, A., , Rey, D., Soares, A.M., Sobrinho, F., Laut, L.M., Frontalini, F., Terroso, D., Miranda, P., Fernández-Fernández. S., Rodrigues, M.A., Figueira, R., Sousa, S.M., Amaral, P. Mahiques, M. and Rocha, F., 2013. The ITRAX core scanner, an useful tool to distinguish anthropic vs climatic influences in lagoon of Aveiro (N Portugal). The main goal of this work is to distinguish anthropic and climatic influences in sediments from the lagoon of Aveiro (Portugal). This study is based on a core (240-cm long) collected in Murtosa Channel. Optical and X-radiographic images and high-resolution elemental profiles were acquired with ITRAX micro-X-ray fluorescence (XRF) core scanner. Samples collected at each ≈3 cm along the core were analysed for grain size and total organic carbon. Furthermore, the fine fraction of selected layers was subjected to geochemical analysis by ICP-MS, after total acid digestion of the sediments, and mineralogical analysis, by XRD techniques. A radiocarbon age was determined by AMS, using molluscs shells collected at a depth of 90 cm. Sediments along the core are composed by fine and medium sand, with several mud layers. Sediments composing the first 100-cm may have been deposited after 1950, as it is indicated by the radiocarbon data, the increasing trend of Zn/Al, Pb/Al and Cu/Al and total concentrations of Zn, Pb, Cu, V, Cr, As and Ni in this interval that therefore might be linked with industrial activities of Chemical Complex of Estarreja. The progressive increase of Si/Al, Cl/Al, Rb/Al, K/Al and Br/Al and reduced Al concentrations, from the base to the top of this core, are interpreted as being related to higher marine influence and greater differences in tidal currents with longer exposition to air of the sediments with the consequent formation of brines favouring minerals precipitation in the area (e.g. anhydrite). These results seem to be a consequence of several works developed over time like: i) dredging to improve the navigation access to the harbour, located in the external sector of the lagoon; ii) the control of the course of some rivers influencing the supply of sediments. The tendency of sea level rise may have also emphasized the gradual increase of marine influence in this area. Fine-grained sections, related to an increase in Al, phyllosilicates, organic matter, pyrite and siderite contents would be attributed to phases of greater supply of fine-sediments during heavy rainfall events by the nearby Antuã river and other streams during negative phases of North Atlantic Oscillation. Higher deposition of organic matter enhanced diagenetic changes with pyrite and siderite formation. In the bottom of the core another record of pollution was unveiled to mining activities at the beginning of 20th century.

Foraminifera, Thecamoebians, and Bacterial Activity in Polluted Intertropical and Subtropical Brazilian Estuarine Systems

ABSTRACT Laut, L.L.M.; Martins, V.; da Silva, F.S.; Crapez, M.A.C.; Fontana, L.F.; Carvalhal-Gomes, S.B.V., and Souza, R.C.C.L., 2016. Foraminifera, thecamoebians, and bacterial activity in polluted intertropical and subtropical Brazilian estuarine systems. This study aims to identify relationships between total organic matter (TOM), bacterial carbon (BC), and metabolic activity in the thecamoebian and foraminifera community of five estuarine regions on the Brazilian coast. Sediment samples were collected from the subtidal zone of five Brazilian estuaries: Potengi, Mataripe Sound, Paraíba do Sul, Suruí, and Itacorubí. A total of 21 thecamoebian species, 29 species of agglutinated foraminifera, and 55 species of calcareous foraminifera were identified. In these estuaries the anaerobic process was dominant. In the Potengi Estuary, located in the NE coast of Brazil, the assemblages showed a decrease in diversity and richness as well as an increase in bacterial carbon concentrations. In the other estuaries the opposite pattern was observed, because they were dominated by agglutinated foraminifera and thecamoebians. Bacterial sulfate-reduction activity promotes acidification of the environment during organic matter degradation, and only calcareous species like Ammonia tepida, Elphidium fimbriatulum, Cribroelphidium poeyanum, Bolivina striatula, Bolivina inflata, and Nonionella opima increase their relative abundance with rising BC and TOM. Miliammina fusca, Haplophragmoides wilberti, and some species of trochamminids are associated positively with bacterial concentrations. Most of the thecamoebians species of genus Difflugia are positively related to BC, but Centropyxis aculeata is more clearly linked with total organic matter.

Recent benthic foraminifera from the Itaipu Lagoon, Rio de Janeiro (southeastern Brazil)

Itaipu Lagoon is located near the mouth of Guanabara Bay and has great importance for recreation to the city of Niteroi, Rio de Janeiro state, Brazil. Several studies have documented foraminiferan diversity at Guanabara Bay, but none in Itaipu Lagoon. Therefore, this study lists and provides images of foraminiferal species collected from Itaipu Lagoon. A total of 35 species belonging to 23 genera were collected, grouped in 17 families and four orders. Ammonia tepida was the species with the highest occurrence. This study represents a baseline work for future investigations.