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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.

Abstract Seabirds are known to play an important role in the geochemical cycling of macronutrients; however, their role in cycling elements of environmental interest has not been investigated. Guano is an important source of marine-derived nutrients and trace metals in seabird nesting areas, but most of the available information on this topic is derived from local studies. In the present study, we used a bioenergetic model to estimate the amounts of cadmium (Cd), mercury (Hg) and lead (Pb) that are deposited via faecal material in seabird colonies worldwide. The findings showed that the seabirds excreted 39.3 Mg (Mg = metric ton or 1000 kg) of Cd, 35.7 Mg of Hg and 27.2 Mg of Pb annually. These amounts are of the same order of magnitude as those reported for other fluxes considered in the geochemical cycling of these elements (e.g. sea-salt spray, cement production, soil loss to oceans). Most of the deposition occurs in circumpolar zones in both hemispheres and, interestingly, high proportions of the metals in the excrements occur in geochemically labile forms, which can be easily leached into coastal waters and assimilated by marine organisms.

Crab and soil samples were seasonally collected at four mangrove sites (Cacha Prego, CP; Ponta Grossa, PG; Ilha de Maré, IM; and Pitinga, PT) in Todos os Santos Bay, in NE Brazil. Total Cu levels in soils ranged from 2.5 to 89.4 mg kg−1, while in crab organs (muscles, hepatopancreas, and gills), Cu ranged from 20 to 1,320 mg kg−1, with the highest concentrations found in the Ilha de Maré population, where soils showed a clear Cu enrichment. Total Cu content did not explain the abnormally high Cu concentrations observed in crabs from Pitinga, where total content in soil was low. Geochemical partitioning indicated that most of the potentially bioavailable Cu was found in the oxidizable fractions, pyrite and organic matter. Pyrite oxidation during the dry season led to increased Cu bioavailability. This process was of relevance in soils of the Pitinga mangrove, where sulfide oxidation led to soil acidification and to an increase in Cu associated with the most labile fractions.

Pollution-induced neurotoxicity is of high concern. This pilot study investigated the potential relationship between the presence of microplastics (MPs) in the brain of 180 wild fish (Dicentrarchus labrax, Platichthys flesus, Mugil cephalus) from a contaminated estuary and the activity of the acetylcholinesterase (AChE) enzyme. MPs were found in 9 samples (5% of the total), all of them from D. labrax collected in the summer, which represents 45% of the samples of this species collected in that season (20). Seventeen MPs were recovered from brain samples, with sizes ranging from 8 to 96 μm. Polyacrylamide, polyacrylic acid and one biopolymer (zein) were identified by Micro-Raman spectroscopy. Fish with MPs showed lower (p ≤ 0.05) AChE activity than those where MPs were not found. These findings point to the contribution of MPs to the neurotoxicity induced by long-term exposure to pollution, stressing the need of further studies on the topic to increase ‘One Health’ protection.

Manganese (Mn) is an abundant element in terrestrial and coastal ecosystems and an essential micronutrient in the metabolic processes of plants and animals. Mn is generally not considered a potentially toxic element due to its low content in both soil and water. However, in coastal ecosystems, the Mn dynamic (commonly associated with the Fe cycle) is mostly controlled by redox processes. Here, we assessed the potential contamination of the Rio Doce estuary (SE Brazil) by Mn after the world’s largest mine tailings dam collapse, potentially resulting in chronic exposure to local wildlife and humans. Estuarine soils, water, and fish were collected and analyzed seven days after the arrival of the tailings in 2015 and again two years after the dam collapse in 2017. Using a suite of solid-phase analyses including X-ray absorption spectroscopy and sequential extractions, our results indicated that a large quantity of MnII arrived in the estuary in 2015 bound to Fe oxyhydroxides. Over time, dissolved Mn and Fe were released from soils when FeIII oxyhydroxides underwent reductive dissolution. Due to seasonal redox oscillations, both Fe and Mn were then re-oxidized to FeIII, MnIII, and MnIV and re-precipitated as poorly crystalline Fe oxyhydroxides and poorly crystalline Mn oxides. In 2017, redox conditions (Eh: −47 ± 83 mV; pH: 6.7 ± 0.5) favorable to both Fe and Mn reduction led to an increase (~880%) of dissolved Mn (average for 2015: 66 ± 130 µg L-1; 2017: 582 ± 626 µg L-1) in water and a decrease (~75%, 2015: 547 ± 498 mg kg−1; 2017: 135 ± 80 mg kg−1) in the total Mn content in soils. The crystalline Fe oxyhydroxides content significantly decreased while the fraction of poorly ordered Fe oxides increased in the soils limiting the role of Fe in Mn retention. The high concentration of dissolved Mn found within the estuary two years after the arrival of mine tailings indicates a possible chronic contamination scenario, which is supported by the high levels of Mn in two species of fish living in the estuary. Our work suggests a high risk to estuarine biota and human health due to the rapid Fe and Mn biogeochemical dynamic within the impacted estuary.

Hypersaline tidal flats (HTF) are ecotones associated with mangrove ecosystems in arid and semiarid coasts. They are predominantly vegetated by halophytes which are related to environmental stabilization and fauna protection. Some plants thrive in HTF by modifying soil biogeochemical conditions at their rhizospheres, expanding across barren soils. Thus, we aimed to study rhizospheric and the adjacent bulk soils of the three most abundant plant species in HTF under a seasonal semiarid climate of northeastern Brazil. We analyzed both rhizospheric and bulk soils of vegetation patches in wet and dry seasons. We found that HTF soils are a heterogeneous system highly influenced by water availability and plant activity. The soils were mostly sandy textured, containing low C and N contents, and hypersaline conditions. Comparing bulk and rhizospheric soils, we concluded that plants changed their own rhizosphere by creating nutrient pools to improve survival under saline conditions. Seasonal changes also affected soil biogeochemical processes in HTF, mainly the bulk soils by changing water availability. Understanding rhizospheric changes by halophytes, their expansion over barren soils, and the amelioration of soil physicochemical conditions, are fundamental to provide support for preservation and management of coastal ecosystems, including HTF.

Seasonality and crab activity affects the nutrients and physicochemical parameters in mangrove soils, thus, affecting the emissions of greenhouse gases, such as nitrous oxide (N2O). Climate change may intensify rainfall and/or enhance droughts, affecting mangroves and associated biota. Crabs are natural soil bioturbators responsible for soil aeration and turnover. We evaluated the effect of Ucides cordatus crab on N2O emissions from mangrove soils under a semiarid climate in Northeastern Brazil. Soil and gas samples were collected over the rainy and dry seasons in crab-naturally-bioturbated and crab-exclusion mangrove plots. We measured the soil’s pH, redox potential, and the total contents of carbon, nitrogen, and sulfur. We found higher N2O emissions in the crab-exclusion sites compared to the bioturbated sites, as well as higher N2O emissions in the rainy season compared to the dry season. The fluxes of N2O (µg m−2 h−1) were 47.3 ± 9.7 and 8.9 ± 0.5 for the crab-exclusion sites, and 36.5 ± 7.8 and 4.5 ± 2.1 for the bioturbated sites (wet and dry seasons, respectively). The soil turning over by macrofauna led to lower N2O fluxes in natural crab-bioturbated areas, and seasonality was the environmental factor that contributed the most to the changes in N2O emissions. Broadly, anthropic activities and seasonality influence nitrogen fate, N2O emissions, and ecological services in coastal ecosystems.

Natural and anthropogenic sources contribute to arsenic contamination in water and human food chain in Andean countries. Human exposure to arsenic via rice consumption is of great concern in countries where this crop is the dominant staple food, and limited information is available on the arsenic contamination on rice in Ecuador. This work was to contribute to the lack of knowledge analysing total arsenic by hydride generation-atomic absorption spectrometry in the samples of white, brown and parboiled rice purchased in Ecuadorian markets and produced in the two main rice wetlands in Ecuador, Guayas and Los Ríos, were carried out. For the samples from Guayas, arsenic concentration in white, brown and parboiled rice were 0.174 ± 0.014, 0.232 ± 0.021, and 0.186 ± 0.017 mg/kg respectively, whereas samples of white rice from Los Ríos showed a total arsenic level of 0.258 ± 0.037 mg/kg. This last arsenic concentration exceeds recommended maximum permissible limit by the FAO/WHO. Obtained data have available to estimate the Ecuadorian dietary exposure revealing serious health risk for population.

The tsscds method, recently developed in our group, discovers chemical reaction mechanisms with minimal human intervention. It employs accelerated molecular dynamics, spectral graph theory, statistical rate theory and stochastic simulations to uncover chemical reaction paths and to solve the kinetics at the experimental conditions. In the present review, its application to solve mechanistic/kinetics problems in different research areas will be presented. Examples will be given of reactions involved in photodissociation dynamics, mass spectrometry, combustion chemistry and organometallic catalysis. Some planned improvements will also be described.

BACKGROUND: Temporomandibular disorders are the most common cause of chronic orofacial pain, but, except where they occur subsequent to trauma, their cause remains unknown. This cross-sectional study assessed chewing function (habitual chewing side) and the differences of the chewing side and condylar path and lateral anterior guidance angles in participants with chronic unilateral temporomandibular disorder. This is the preliminary report of a randomized trial that aimed to test the effect of a new occlusal adjustment therapy. METHODS: The masticatory function of 21 randomly selected completely dentate participants with chronic temporomandibular disorders (all but one with unilateral symptoms) was assessed by observing them eat almonds, inspecting the lateral horizontal movement of the jaw, with kinesiography, and by means of interview. The condylar path in the sagittal plane and the lateral anterior guidance angles with respect to the Frankfort horizontal plane in the frontal plane were measured on both sides in each individual. RESULTS: Sixteen of 20 participants with unilateral symptoms chewed on the affected side; the concordance (Fisher's exact test, P = .003) and the concordance-symmetry level (Kappa coefficient κ = 0.689; 95% confidence interval [CI], 0.38 to 0.99; P = .002) were significant. The mean condylar path angle was steeper (53.47(10.88) degrees versus 46.16(7.25) degrees; P = .001), and the mean lateral anterior guidance angle was flatter (41.63(13.35) degrees versus 48.32(9.53) degrees P = .036) on the symptomatic side. DISCUSSION: The results of this study support the use of a new term based on etiology, "habitual chewing side syndrome", instead of the nonspecific symptom-based "temporomandibular joint disorders"; this denomination is characterized in adults by a steeper condylar path, flatter lateral anterior guidance, and habitual chewing on the symptomatic side.