Contrasting plant-induced changes in heavy metals dynamics: Implications for phytoremediation strategies in estuarine wetlands.

Wetland plants play a crucial role in regulating soil geochemistry, influencing heavy metal (HM) speciation, bioavailability, and uptake, thus impacting phytoremediation potential. We hypothesized that variations in HM biogeochemistry within estuarine soils are controlled by distinct estuarine plant species. We evaluated the soils (pH, redox potential, rhizosphere pH, HM total concentration, and geochemical fractionation), plant parts (shoot and root), and iron plaques of three plants growing in an estuary affected by Fe-rich mine tailings. Though the integration of multiple plant and soil analysis, this work emphasizes the importance of considering geochemical pools of HM for predicting their fate. Apart from the predominance of HM associated with Fe oxides, Typha domingensis accumulated the highest Cr and Ni contents in their shoots (> 100 mg kg-1). In contrast, Hibiscus tiliaceus accumulated more Cu and Pb in their roots (> 50 mg kg-1). The differences in rhizosphere soil conditions and root bioturbation explained the different potentials between the plants by altering the soil dynamics and HM's bioavailability, ultimately affecting their uptake. This study suggests that Eleocharis acutangula is not suitable for phytoextraction or phytostabilization, whereas Typha domingensis shows potential for Cr and Ni phytoextraction. In addition, we first showed Hibiscus tiliaceus as a promising wood species for Cu and Pb phytostabilization.

Seasonal drives on potentially toxic elements dynamics in a tropical estuary impacted by mine tailings.

This study investigates the impact of seasonality on estuarine soil geochemistry, focusing on redox-sensitive elements, particularly Fe, in a tropical estuary affected by Fe-rich mine tailings. We analyzed soil samples for variations in particle size, pH, redox potential (Eh), and the content of Fe, Mn, Cr, Cu, Ni, and Pb. Additionally, sequential extraction was employed to understand the fate of these elements. Results revealed dynamic changes in the soil geochemical environment, transitioning between near-neutral and suboxic/anoxic conditions in the wet season and slightly acidic to suboxic/oxic conditions in the dry season. During the wet season, fine particle deposition (83%) rich in Fe (50 g kg-1), primarily comprising crystalline Fe oxides, occurred significantly. Conversely, short-range ordered Fe oxides dominated during the dry season. Over consecutive wet/dry seasons, substantial losses of Fe (-55%), Mn (-41%), and other potentially toxic elements (Cr: -44%, Cu: -31%, Ni: -25%, Pb: -9%) were observed. Despite lower pseudo-total PTE contents, exchangeable PTEs associated with carbonate content increased over time (Cu: +188%, Ni: +557%, Pb: +99%). Modeling indicated climatic variables and short-range oxides substantially influenced PTE bioavailability, emphasizing the ephemeral Fe oxide control during the wet season and heightened ecological and health risks during the dry seasons.

Rare Earth Element Accumulation in Fiddler Crabs (Minuca rapax) from the Rio Doce Tropical Estuary Strongly Affected by Mine Tailings Following the Fundão Disaster.

A mining tailing dam rupture in Brazil in November 2015 released millions of tons of mining waste into the Rio Doce ecosystem, leading to long-term aquatic ecosystem impacts. Although multiple lines of evidence indicate tailings associations with potentially toxic elements in estuarine sediments and biological impact and bioaccumulation pathways in fishes, the extent of contamination in base benthic species is still largely unknown. Moreover, Rare Earth Elements (REE) have not received any attention in this regard. This study assessed REE in fiddler crabs (Minuca rapax) sampled from the Rio Doce estuary in 2017, nearly 2 years after the disaster. The ΣREE in crab hepatopancreas and muscle were high (327.83 mg kg-1 w.w. and 33.84 mg kg-1 w.w., respectively, compared to other assessments in crabs, indicating a preference for REE bioaccumulation in the hepatopancreas compared to muscle. Neodimium, La, and Ce were detected at the highest concentrations. The REE from the Rio Doce Basin were, thus, transported and deposited in the estuary with the mine tailings slurry, leading to bioaccumulation in crabs. This may lead to trophic effects and other ecological impacts not readily measured by typical impact assessment studies, revealing an invisible and not typically acknowledged damage to the Rio Doce estuary.

In Vitro and In Silico Evaluation of Red Algae Laurencia obtusa Anticancer Activity.

Studies estimate that nearly 2 million new cases of gastric cancer will occur worldwide during the next two decades, which will increase mortality associated with cancer and the demand for new treatments. Marine algae of the Laurencia genus have secondary metabolites known for their cytotoxic action, such as terpenes and acetogenins. The species Laurencia obtusa has demonstrated cytotoxicity against many types of tumors in previous analyses. In this study, we determined the structure of terpenes, acetogenins, and one fatty acid of Laurencia using mass spectrometry (ESI-FT-ICR/MS). In vitro cytotoxicity assays were performed with adenocarcinoma gastric cells (AGS) to select the most cytotoxic fraction of the crude extract of L. obtusa. The Hex:AcOEt fraction was the most cytotoxic, with IC50 9.23 µg/mL. The selectivity index of 15.56 shows that the Hex:AcOEt fraction is selective to cancer cells. Compounds obtained from L. obtusa were tested by the analysis of crystallographic complexes. Molecular docking calculations on the active site of the HIF-2α protein showed the highest affinity for sesquiterpene chermesiterpenoid B, identified from HEX:AcOEt fraction, reaching a score of 65.9. The results indicate that L. obtusa presents potential compounds to be used in the treatment of neoplasms, such as gastric adenocarcinoma.

Contrasting modes of mitochondrial genome evolution in sister taxa of wood-eating marine bivalves (Teredinidae and Xylophagaidae).

The bivalve families Teredinidae and Xylophagaidae include voracious consumers of wood in shallow and deep-water marine environments, respectively. The taxa are sister clades whose members consume wood as food with the aid of intracellular cellulolytic endosymbionts housed in their gills. This combination of adaptations is found in no other group of animals and was likely present in the common ancestor of both families. Despite these commonalities, the two families have followed dramatically different evolutionary paths with respect to anatomy, life history and distribution. Here we present 42 new mitochondrial genome sequences from Teredinidae and Xylophagaidae and show that distinct trajectories have also occurred in the evolution and organization of their mitochondrial genomes. Teredinidae display significantly greater rates of amino acid substitution but absolute conservation of protein-coding gene order, whereas Xylophagaidae display significantly less amino acid change but have undergone numerous and diverse changes in genome organization since their divergence from a common ancestor. As with many bivalves, these mitochondrial genomes encode two ribosomal RNAs, 12 protein coding genes, and 22 tRNAs; atp8 was not detected. We further show that their phylogeny, as inferred from amino acid sequences of 12 concatenated mitochondrial protein-coding genes, is largely congruent with those inferred from their nuclear genomes based on 18S and 28S ribosomal RNA sequences. Our results provide a robust phylogenetic framework to explore the tempo and mode of mitochondrial genome evolution and offer directions for future phylogenetic and taxonomic studies of wood-boring bivalves.

Degraded mangroves as sources of trace elements to aquatic environments.

Mangrove forests have been reported as sinks for metals because of the immobilization of these elements in their soils. However, climate change may alter the functioning of these ecosystems. We aimed to assess the geochemical dynamics of Mn, Cu, and Zn in the soils of a mangrove forest dead by an extreme weather event in southeastern Brazil. Soil samples were collected from dead and live mangroves adjacent to each other. The physicochemical parameters (total organic carbon, redox potential, and pH), total metal content, particle size, and metal partitioning were determined. Distinct changes in the soil geochemical environment (establishment of suboxic conditions) and a considerable loss of fine particles was caused by the death of the mangroves. Our results also showed a loss of up to 93 % of metals from soil. This study highlights the paradoxical role of mangroves as potential metal sources in the face of climate change.

Iron hazard in an impacted estuary: Contrasting controls of plants and implications to phytoremediation.

Due to its abundance and role as a micronutrient for plants iron (Fe) is rarely perceived as a contaminant. However, in redox active environments, Fe bioavailability increases sharply representing an environmental risk. In this study, a recent catastrophic mining dam failure is used as a field framework to evaluate the role of wetland plants on Fe biogeochemistry and assess their potential for phytoremediation programs. To achieve these objectives, a Fe geochemical partitioning and the concentration of Fe in different plant compartments (iron plaque on root surfaces, roots, and leaves) were determined in two sites vegetated by different wetland species. Soils exhibited contrasting Fe biogeochemical dynamics. Lower pseudo-total contents and more reactive Fe oxides were observed in the soil vegetated by Typha domingensis. Iron plaque was present on both species but more concentrated in Fe in T. domingensis. T. domingensis showed Fe shoot concentrations (3874 mg kg-1) 10-fold higher than in Hibiscus tiliaceus, which prevented Fe absorption through iron plaque formation and root accumulation. In conclusion, contrasting biogeochemical effects on Fe (e.g., rhizosphere acidification) lead to different phytoremediation abilities. T. domingensis showed a high potential for Fe phytoremediation on sites affected by Fe-enriched wastes and should be tested in assisted phytoremediation approaches.

Mine tailings in a redox-active environment: Iron geochemistry and potential environmental consequences.

Iron (Fe) oxyhydroxides provide many functions in soils, mainly owing to their large surface area and high surface charge density. The reactivity of Fe oxyhydroxides is function of their mineralogical characteristics (e.g., crystallinity degree and crystal size). Detailed studies of these features are essential for predicting the stability and reactivity of these minerals within soil and sediments. The present study aimed to evaluate geochemical changes in Fe-rich tailings after the world's largest mining disaster in SE Brazil (in 2015) and to predict the potential environmental implications for the estuary. The mineralogical characteristics of the tailings were studied at three different times (2015, 2107, and 2019) to assess how an active redox environment affects Fe oxyhydroxides and to estimate the time frame within which significant changes occur. The study findings indicate a large decrease in the Fe oxyhydroxides crystallinity, which were initially composed (93%) of highly crystalline Fe oxyhydroxides (i.e., goethite and hematite) and 6.7% of poorly crystalline Fe oxyhydroxides (i.e., lepidocrocite and ferrihydrite). Within 4 years the mineralogical features of Fe oxyhydroxides had shifted, and in 2019 poorly crystalline Fe oxyhydroxides represented 47% of the Fe forms. Scanning electron microscope micrographs and the mean crystal size evidenced a decrease in particle size from 109 nm to 49 nm for goethite in the d111 direction. The changes in mean crystal size increased the reactivity of Fe oxyhydroxides, resulting in a greater number of interactions with cationic and anionic species. The decreased crystallinity and increased reactivity led to the compounds being more susceptible to reductive dissolution. Overall, the findings show that the decrease in crystallinity along with higher susceptibility to reductive dissolution of Fe oxyhydroxides can affect the fate of environmentally detrimental elements (e.g., phosphorus and trace metals) thereby increasing the concentration of these pollutants in estuarine soils and waters.

Iron ore tailings as a source of nutrients to the coastal zone.

The Fundão dam rupture was one of the largest environmental disasters worldwide and released millions of m3 of iron ore tailings into the Doce River basin in southeastern Brazil. Here we assessed the supply of dissolved nutrients associated to tailings in the Doce River estuary and its adjacent coastal zone. First, we observed an acute increase in dissolved silicates (From 16.26 µM to 175.47 µM) and nitrate (From 5.56 µM to 50.69 µM) in the estuary when compared to days prior to the event. Coastal marine ecosystems showed significant concentrations of nitrite (From 0.72 µM to 2.99 µM) and phosphate (From 0.09 µM to 2.30 µM) one year after the disaster, which we attribute mainly to nutrient recycling. The chronic effects include an increase in nutrient load to the coastal zone with a predominance of nitrogenous species, which may increase the limitation of phosphorus and silica to marine primary production.

Time-sequence development of metal(loid)s following the 2015 dam failure in the Doce river estuary, Brazil.

In the context of the Doce river (Southeast Brazil) Fundão dam disaster in 2015, we monitored the changes in concentrations of metal(loid)s in water and sediment and their particulate and dissolved partitioning over time. Samples were collected before, during, and after the mine tailings arrival to the Doce river estuary (pre-impact: 12, 10, 3 and 1 day; acute stage: tailing day - TD and 1 day after - DA; chronic stage: 3 months and 1 year post-disaster). Our results show that metal(loid) concentrations significantly increased with time after the disaster and changed their chemical partitioning in the water. 35.2 mg Fe L-1 and 14.4 mg Al L-1 were observed in the total (unfiltered) water during the acute stage, while aqueous Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Se and Zn concentrations all exceeded both Brazilian and international safe levels for water quality. The Al, Fe and Pb partitioning coefficient log (Kd) decrease in the acute stage could be related to the high colloid content in the tailings. We continued to observe high concentrations for Al, Ba, Cd, Cr, Cu, Fe, V and Zn mainly in the particulate fraction during the chronic stage. Furthermore, the Doce river estuary had been previously contaminated by As, Ba, Cr, Cu, Mn, Ni and Pb, with a further increase in sediment through the tailing release (e.g. 9-fold increase for Cr, from 3.61 ± 2.19 µg g-1 in the pre-impact to 32.16 ± 20.94 µg·g-1 in the chronic stage). Doce river sediments and original tailing samples were similar in metal(loid) composition for Al, As, Cd, Cr, Cu, Fe, V and Zn. As a result, these elements could be used as geochemical markers of the Fundão tailings and considering other key parameters to define a baseline for monitoring the impacts of this environmental disaster.

The collapse of mangrove litterfall production following a climate-related forest loss in Brazil.

Drought periods may change mangrove litterfall production through water deprivation and increasing tree evapotranspiration, but these impacts have been rarely estimated. In Brazil, an intense drought and strong winds impacted mangrove forests leading to mass tree mortality in 2016, suggesting that forest productivity also declined rapidly. Fifteen months after the initial impact, we started to monitor and quantify litterfall production in paired transects from disturbed and undisturbed mangroves. The litterfall production of the undisturbed forests (575 ± 28 Kg C ha-1 y-1) was 31- to 3-fold higher than that at the disturbed mangrove forests (18 to 169 Kg C ha-1 y-1). The strong decline in litterfall production may have implications to the export of nutrients to estuarine ecosystems. Our baseline suggests that mangrove forests are greatly vulnerable to climate impacts and that the litterfall production collapse in dead mangrove forests may impair marine ecosystem food webs.

Drought effects on tropical estuarine benthic assemblages in Eastern Brazil.

Climate change will increase the frequency and intensity of extreme weather events with potential effects in coastal and estuarine ecosystems. During drought periods, higher salinity and temperature can directly impact estuarine benthic assemblages through physiological stress and alteration of sedimentary habitats, but these effects are poorly evaluated to date. Here we report a 14-month monitoring of benthic assemblages in a tropical estuary in the Eastern Brazil Marine Ecoregion during the severe drought period of 2015/2016. The drought in Eastern Brazil resulted in a decrease of estuarine mean sediment particle size and concurrent changes in macrofaunal benthic assemblages during the driest months. We also observed a 3-fold reduction on macrofaunal abundance with dominance of surface-dwelling Magelonid, Sternaspid, Capitellid and Oligochaeta annelids. The changes in macrofaunal structure during the severe drought also decreased the community bioturbation potential (BPc) by 5-fold, if compared to pre-drought periods. We argue that the projected increases in the frequency and severity of climatic events, such as observed during severe droughts worldwide, will greatly change the benthic fauna and their ecological functions in tropical estuarine ecosystems.

Extreme weather impacts on tropical mangrove forests in the Eastern Brazil Marine Ecoregion.

Extreme weather events are likely to become more frequent in the 21st century bringing significant impacts to coastal ecosystems. However, the capacity to detect and measure those impacts are still limited, with effects largely unstudied. In June 2016, a hailstorm with wind gusts of over 100 km·h-1 caused an unprecedented mangrove dieback on Eastern Brazil. To quantify the scale of impact and short-term recovery of mangroves (15-mo), we used satellite imagery and field sampling to evaluate changes in forest structure in control and impacted areas after the hailstorm. Satellite imagery revealed mangrove dieback in over 500 ha, corresponding to 29.3% of the total forest area suddenly impacted after the hailstorm. Fifteen months after the hailstorm, some impacted areas show an initial recovery, while others continued to degrade. The El Niño years of 2014-2016 created mild drought conditions in Eastern Brazil. As observed in wetlands of semi-arid regions during the same period, mangrove recovery may have been impaired by continued physiological stress and climate change effects. Economic losses in the study site from typical mangrove ecosystem services including food provision, climate regulation, raw materials and nurseries are estimated to at least US$ 792,624 yr-1. This is the first evidence of an extreme weather impact on mangroves in Brazil that typically provide unique ecological and economic subsistence to coastal populations. Our results reveal that there is a pressing need for long-term monitoring and climate change adaptation actions for coastal wetlands in Brazil, and to provide broad estimates of ecosystem values associated with these ecosystems given many areas are already experiencing chronic stress from local impacts, drought and high temperatures.

Mangrove clearing impacts on macrofaunal assemblages and benthic food webs in a tropical estuary.

Despite over 21,000ha of mangrove forests being removed per year in Brazil, ecological changes following mangrove deforestation have been overlooked. Here we evaluated changes in benthic macrofaunal assemblages and food-webs at a mangrove removal and natural sites in a tropical estuary in Eastern Brazil. The impacted site had coarser sediment particle sizes suggesting significant changes in sedimentation processes after forest clearing. Spatial differences in macrofaunal abundance, biomass and diversity were not directly associated with the removal of mangrove forests, supporting recolonization of impacted areas by estuarine fauna. However, benthic assemblage composition, infaunal δ13C signatures and food-web diversity markedly differed at the impacted site being strongly related to sedimentary changes. The loss of infaunal trophic diversity that followed mangrove removal suggests that large-scale forest clearing may impact estuarine food webs, with potential consequences to nearby coastal ecosystems given the high clearing rate of mangrove forests in Brazil.

The impacts of the Samarco mine tailing spill on the Rio Doce estuary, Eastern Brazil.

Over 50 million cubic meters of mining tailings were released in the Rio Doce basin after the collapse of the Fundão dam (Samarco) in November 2015. Predicting significant impacts on the Rio Doce estuary, we sampled sediments to investigate short-term impacts on the benthic assemblages and trace metal accumulation on estuarine sediments. With the arrival of the tailing plumes in the estuary, we detected a predominance of clay particles and increased trace metal concentrations of up to 5 times in some areas. The rapid sedimentation after the impact also impacted estuarine macrofaunal assemblages through loss surface-dwelling taxa. As expected, the impacts on benthic assemblages observed up to 3days after the arrival of tailings were not clearly associated with trace metal concentrations, but long-term effects need to be studied. We recommend that the high spatial variability within the estuary be considered in future impact assessment studies.