Disentangling natural vs. anthropogenic induced environmental variability during the Holocene: Marambaia Cove, SW sector of the Sepetiba Bay (SE Brazil).

Multiproxy approach based on textural, mineralogical, geochemical, and microfaunal analyses on a 176-cm-long core (SP8) has been applied to reconstruct the Holocene paleoenvironmental changes and disentangling natural vs. anthropogenic variability in Marambaia Cove of the Sepetiba Bay (SE Brazil). Sepetiba Bay became a lagoonal system due to the evolution and development of the Marambaia barrier island during the Holocene and the presence of an extensive river basin. Elemental concentrations from pre-anthropogenic layers from the nearby SP7 core have been used to estimate the baseline elemental concentrations for this region and to determine metals enrichment factors (EF), pollution load index (PLI), and sediment pollution index (SPI). Record of the core SP8 provides compelling evidence of the lagoon evolution differentiating the effects of potentially toxic elements (PTEs) under natural vs. anthropic forcing in the last ~ 9.5 ka BP. The study area was probably part of coastal sand ridges between ≈ 9.5 and 7.8 ka BP (radiocarbon date). Events of wash over deposited allochthonous material and organic matter between ≈ 8.6 and 7.8 ka. Climatic event 8.2 ka BP, in which the South American Summer Monsoon was intensified in Brazil causing higher rainfall and moisture was scored by an anoxic event. Accumulation of organic matter resulted in oxygen depletion and even anoxia in the sediment activating biogeochemical processes that resulted in the retention of potentially toxic elements (PTEs). After ≈ 7.8 ka BP at the onset of the Holocene sea-level rise, a marine incursion flooded the Marambaia Cove area (previously exposed to subaerial conditions). Environmental conditions became favorable for the colonization of benthic foraminifera. The Foram Stress Index (FSI) and Exp(H'bc) indicate that the environmental conditions turned from bad to more favorable since ≈ 7.8 ka BP, with maximum health reached at ≈ 5 ka BP, during the mid-Holocene relative sea-level highstand. Since then, the sedimentological and ecological proxies suggest that the system evolved to an increasing degree of confinement. Since ≈ 1975 AD, a sharp increase of silting, Cd, Zn, and organic matter also induced by anthropic activities caused major changes in foraminiferal assemblages with a significant increase of Ammonia/Elphidium Index (AEI), EF, and SPI values and decreasing of FSI and Exp(H'bc) (ecological indicators) demonstrating an evolution from "moderately polluted" to "heavily polluted" environment (bad ecological conditions), under variable suboxic conditions. Thus, core SP8 illustrates the most remarkable event of anthropogenic forcing on the geochemistry of the sediments and associated pollution loads and its negative effect on benthic organisms.

Long-term eutrophication and contamination of the central area of Sepetiba Bay (SW Brazil).

This work sheds light on the recent evolution (≈1915-2015 AD) of Sepetiba Bay (SB; SE Brazil), a subtropical coastal lagoon on the southwestern Brazilian coast, based on a multiproxy approach. Variations in geochemical proxies as well as textural, mineralogical and geochronological data allow us to reconstruct temporally constrained changes in the depositional environments along the SP3 sediment core collected from the central area of SB. At the beginning of the twentieth century, the substrate of the study site was composed of coarse-grained sediments, largely sourced from felsic rocks of proximal areas and deposited under moderate to strong shallow marine hydrodynamics. Since the 1930s, the study area has undergone silting and received high contributions of materials from mafic rocks sourced by river basins. The SP3 core reveals a shallowing-upward sequence due to human-induced silting with significant eutrophication since the middle of 1970, which was caused by significant enrichment of organic matter that was provided by not only marine productivity but also continental and human waste. In addition, the sediments deposited after 1980 exhibit significant enrichment and are moderately to strongly polluted by Cd and Zn. Metals were dispersed by hydrodynamics from the source areas, but diagenetic processes promoted their retention in the sediments. The potential ecological risk index (PERI) indicates that the level of high (considerable) ecological risk is in sediments deposited in ≈1995 (30-32 cm; subsurface). The applied methodology allowed us to understand the thickness of the bottom sediment affected by eutrophication processes and contaminants. Identical methodologies can be applied in other coastal zones, and can provide useful information to decision makers and stakeholders that manage those areas.

Ecological quality status of the NE sector of the Guanabara Bay (Brazil): A case of living benthic foraminiferal resilience.

The ecological quality status of the NE region of the Guanabara Bay (SE Brazil), one of the most important Brazilian embayments, is evaluated. For this purpose, sediment samples from in the inner of the Guanabara Bay (GB) were collected and analyzed (grain-size, mineralogy, geochemistry and living foraminifera). In this study, it is hypothesized that the potentially toxic elements (PTEs) concentrations, in solution and associated with organic matter (OMPTEs, potential nutrient source), may represent two potential pathways to impact benthic foraminifers. A multiproxy approach applied to complex statistical analyses and ecological indexes shows that the study area is, in general, eutrophic (with high organic matter and low oxygen content), polluted by PTEs and oil. As a consequence, foraminifera are not abundant and their assemblages are poorly diversified and dominated by some stress-tolerant species (i.e., Ammonia tepida, Quinqueloculina seminula, Cribroelphidium excavatum). The results allow us to identify a set of species sensitive to eutrophication and OMPTEs. Factors such as the increase of organic matter contents and OMPTEs and, in particular of Zn, Cd and Pb, the oxygen depletion and the presence of oil, altogether contribute to a marked reduction in the abundance and diversity of foraminifera. Ammonia-Elphidium Index and the Foram Stress Index confirm that the NE zone of GB is, in general, "heavily polluted", with "poor ecological quality status" and experiences suboxic to anoxic conditions. In light of it, special attention from public authorities and policymakers is required in order to take immediate actions to enable its environmental recovery.

Assessment of Clayey Peloid Formulations Prior to Clinical Use in Equine Rehabilitation.

Clays are natural ingredients used to prepare therapeutic cataplasms suitable for topical application. The knowledge about these formulations and their preparations to be applied on humans and animals has been orally transmitted since ancient times. Several empirical methods using clays have demonstrated fast and effective results in the reduction of the inflammatory response and the formation of edemas in horse limbs. The use of traditional and alternative medicine, such as pelotherapy, is now becoming more popular in veterinarian medical practice, alone or combined with other therapies in horse muscle and tendon rehabilitation. This study characterizes the use of commercial equine clays and an old therapeutic clay cataplasm formulation, using acetic acid, to treat tendon injuries in horses. This work might contribute to a major database characterization of clays used empirically on equine health, the potential of dermal absorption, the risks of exposure to some toxic elements, and safety assessment for these formulations. The present study was carried out to characterize the suitability of four commercial equine clays (Group II) and a protocoled healing mixture: "clay acetic acid cataplasm", (Group III), to treat tendon injuries in horses. In this mixture, three conventional "green" clays (Group I) without any mineralogical specificity were used and blended with acetic acid. The mineralogical composition was determined through X-ray powder diffraction and X-ray fluorescence data. To determine the performance of the samples, cooling kinetics, oil absorption, expandability, and specific surface area were measured. According to the mineralogical composition, Group I was mainly composed of carbonates and silicates, while Group II was much richer in silicates with the main clay minerals kaolinite and illite. Group II exhibited the highest values for As, Pb, Cr, Ni, and Zn, considered potentially toxic. Both groups showed low cation exchange capacities and exchanged mainly Ca2+, with the exception of VET.1 and VET.7, which also highlight Na+, and VET.5 and VET.6, which have K+ as an exchangeable main cation. The addition of acetic acid (Group III) does not reveal any significant chemical changes. The results confirm that both clay groups are adequate for the therapeutic propose. They have good plastic properties (skin adherence), good oil absorptive capabilities (cleaning), and exchange an essential physiological element, calcium. Group II has prior industrial preparation, which is probably why it showed better results. Group I presented lower heat retention capacity and higher abrasiveness, which could be improved using cosmetic additives. The clinical benefit of the "clay acetic acid cataplasm" (Group III) could be the systemic anti-inflammatory effect established by the acetic acid.

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.