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.

How do replanted mangroves affect phosphorus dynamics in their soils?

Phosphorus is a limiting element for the productivity of mangroves, which in turn are important ecosystems in regulating nutrients cycle and climate change by sequestering carbon (C). Despite this, there is an intense process of degradation in these environments. In addition to providing socio-environmental services, mangrove replanting can also alter the dynamics of nutrients in soils. Therefore, this study aims to understand the changes in soil phosphorus (P) fractions after a mangrove restoration. Soil samples from an unvegetated area (NV), a mature mangrove (R) and 7 and 9 year old replanted mangroves at SE-Brazil (APA Guapi-mirim, Rio de Janeiro state) were collected and analyzed to characterize the redox conditions (Eh), pH, and iron (Fe) fractionation, Total Organic Carbon (TOC) contents and P fractionation (exchangeable P; P associated with reducible Fe and Mn oxyhydroxides; associated with Al silicates and hydroxides; associated with humic acids; associated with Ca and Mg; associated with humin). The results indicate an increase in TOC as the age of the mangrove restoration increases (from 8.6 to 17.9%). The pH values were significantly lower, reaching very acidic values, associated with an increase in Eh. Both parameters also showed strong seasonal variation, with a drop in Eh during the wet period (from 165% to -46%) and an increase in pH in the same period (from 6.0 to 6.7). Regarding P fractionation, the main P pool was organic P forms, which showed the highest concentrations in all studied sites. Unvegetated areas showed higher organic P forms (NV: 108.8 µg g-1) than vegetated areas (M7: 55.7 µg g-1, M9: 83.6 µg g-1, R: 87.3 µg g-1). Vegetated sites also showed lower levels of the PEx, PFeMn and Papatite fractions (total forest mean: 2.4 µg g-1, 5.8 µg g-1, 3.0 µg g-1, respectively). Besides no clear trend on P fractionation through seasons and forest age, pseudo-total P increased following the forest recovery (e.g. M7

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.

From waste to soil: Technosols made with construction and demolition waste as a nature-based solution for land reclamation.

Population growth has driven an increased demand for solid construction materials, leading to higher amounts of construction and demolition waste (C&DW). Efficient strategies to manage this waste include reduction, reuse, and recycling. Technosols-soils engineered from recycled waste-can potentially help with environmental challenges. However, there is a critical need to explore the potential of Technosols constructed with C&DW for land reclamation, through the growth of native vegetation. The objective of this study was to investigate this potential by studying two Brazilian native tree species (Guazuma ulmifolia and Piptadenia gonoacantha). Technosols were created using C&DW, with and without organic compost and a liquid biofertilizer. A soil health index (SHI) was applied to evaluate the soil quality regarding physical, chemical, and biological indicators of Technosols compared to a control soil (Ferralsol). The results showed that P. gonoacantha plants presented the same height and total biomass in all treatments, while G. ulmifolia plants exhibited greater height and total biomass when grown in Technosols. The enhanced plant development in the Technosols was primarily associated with higher cation exchangeable capacity and nutrients concentration in plant tissues. Technosols with added compost provided higher fertility and total organic carbon. Additionally, Technosols presented higher SHI (∼0.68) compared to control (∼0.38) for both studied species. Our experiment reveals that construction and demolition waste (C&DW) have significant potential to form healthy Technosols capable of supporting the growth of native Brazilian trees. This approach offers a promising alternative for addressing C&DW disposal challenges while serving as a nature-based solution for land reclamation.

Litho-climatic characteristics and its control over mangrove soil geochemistry: A macro-scale approach.

Brazil hosts an extensive coastal area, marked by a great diversity of geoenvironments. The present study evaluated the role of geoclimatic factors in the geochemistry of mangrove soils by using wet extractions and several physical and chemical parameters. Soil samples were collected in 11 mangrove forests from NE (n = 94) and SE Brazil (n = 230). Our results show an important effect of the surrounding geology and climate on the geochemistry of the mangrove soils. NE mangroves are dominated by suboxic soils (mean: Eh of +150 ± 174 mV and pH 7.1 ± 0.5, respectively) while anoxic conditions prevail in the SE mangrove soils (mean: Eh -46 ± 251 mV and pH 6.5 ± 0.5). In the NE region, a period of several months without rainfall and high temperatures leads to soil suboxic conditions. Conversely, at the SE coast, the surrounding mountain range contributes to well-distributed rain favoring anoxic conditions. The contrasting geochemical environment caused differences in the geochemistry of elements such as C, Fe, and S. Significantly higher Fe (193 ± 24 µmol g-1) and organic carbon contents (6.9 ± 7.1%) were recorded in the SE coast. The higher organic carbon contents are possibly related to Fe organo-mineral associations. These differences are ultimately associated with the contrasting geological surroundings (crystalline massifs at the SE and the iron poor sedimentary formations at the NE). The higher contents of reactive Fe and organic carbon also triggered more intense pyritization in the SE mangroves (pyritic Fe: 93 ± 63 µmol g-1). Our results demonstrate that climate and geological surroundings create identifiable patterns at a regional level and, thus, studies should take these factors into account on future global modelling approaches.

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.

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.

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.

Soil Organic Matter Responses to Mangrove Restoration: A Replanting Experience in Northeast Brazil.

Mangroves are among the most relevant ecosystems in providing ecosystem services because of their capacity to act as sinks for atmospheric carbon. Thus, restoring mangroves is a strategic pathway for mitigating global climate change. Therefore, this study aimed to examine the organic matter dynamics in mangrove soils during restoration processes. Four mangrove soils under different developmental stages along the northeastern Brazilian coast were studied, including a degraded mangrove (DM); recovering mangroves after 3 years (3Y) and 7 years (7Y) of planting; and a mature mangrove (MM). The soil total organic carbon (CT) and soil carbon stocks (SCSs) were determined for each area. Additionally, a demineralization procedure was conducted to assess the most complex humidified and recalcitrant fractions of soil organic matter and the fraction participating in organomineral interactions. The particle size distribution was also analyzed. Our results revealed significant differences in the SCS and CT values between the DM, 3Y and 7Y, and the MM, for which there was a tendency to increase in carbon content with increasing vegetative development. However, based on the metrics used to evaluate organic matter interactions with inorganic fractions, such as low rates of carbon enrichment, C recovery, and low C content after hydrofluoric acid (HF) treatment being similar for the DM and the 3Y and 7Y-this indicated that high carbon losses were coinciding with mineral dissolution. These results indicate that the organic carbon dynamics in degraded and newly planted sites depend more on organomineral interactions, both to maintain their previous SCS and increase it, than mature mangroves. Conversely, the MM appeared to have most of the soil organic carbon, as the stabilized organic matter had a complex structure with a high molecular weight and contributed less in the organomineral interactions to the SCS. These results demonstrate the role of initial mangrove vegetation development in trapping fine mineral particles and favoring organomineral interactions. These findings will help elucidate organic accumulation in different replanted mangrove restoration scenarios.

Nitrogen mineralization and eutrophication risks in mangroves receiving shrimp farming effluents.

Nitrogen (N) inputs originated from shrimp farming effluents were evaluated for potential changes in the net N mineralization for mangrove soils from Northeastern Brazil. Our study provides notable information and assessment for the potential enhancement of N mineralization in preserved and shrimp-impacted semi-arid mangrove soils of the Jaguaribe River estuary, which is one of the largest shrimp producers of Brazil, using an analytical and daily tidal variation experimental approach. Nitrogen-rich effluents promoted a significant (p value < 0.001) increase of the total soil N content (1998 ± 201 mg kg-1 on average) compared with the preserved sites (average: 1446 ± 295 mg kg-1). The effluents also increased the N mineralization in the shrimp-impacted sites (N-min: 86.6 ± 37.5 mg kg-1), when compared with preserved mangroves (N-min: 56.5 ± 23.8 mg kg-1). Over a daily tidal variation experiment, we found that just 30% (36.2 ± 20.6 mg kg-1) of mineralized N remains stored in the soil, whereas 70% (102.9 ± 38.8 mg kg-1) was solubilized in tidal waters. Therefore, the N mineralization process may trigger eutrophication by increasing N inorganic bioavailability in mangrove soils receiving N-rich effluents from shrimp ponds, which in turn might increase primary producers' activity. This approach has not been studied so far in semi-arid mangroves, where the shrimp farming activity is one of the most important economic activities.

Phosphorus enriched effluents increase eutrophication risks for mangrove systems in northeastern Brazil.

Discharge of effluents loaded with phosphorus (P) from anthropogenic activities constitutes serious eutrophication risks in marine and terrestrial ecosystems, including mangroves. Three mangroves in NE-Brazil were studied to evaluate the impact of P-rich-effluents from shrimp farming and domestic sewage, in relation to a control area (natural mangrove). Soil phosphorus fractionation and water chemical analysis were performed to assess potential pollution. We observed the most labile P forms increased gradually and significantly from control to sewage to shrimp farm impacted mangroves as observed by increasingly dissolved orthophosphate (PO43-) content in water and the exchangeable/soluble P (Exch-P) extracted from soils, which is supported by the discriminant analysis. Exch-P results were correlated to Humic-Acid-P, which can release more labile P forms when mineralized. Our results demonstrate a substantial impact of aquiculture and sewage effluents in mangroves at both organic and inorganic P fractions, raising important concerns regarding pollution for these marine ecosystems.

Are acid volatile sulfides (AVS) important trace metals sinks in semi-arid mangroves?

Acid-volatile sulfides (AVS) formation and its role on trace metals bioavailability were studied in semi-arid mangroves. The semi-arid climatic conditions at the studied sites, marked by low rainfall and high evapotranspiration rates, clearly limited the AVS formation (AVS contents varied from 0.10 to 2.34µmolg-1) by favoring oxic conditions (Eh>+350mV). The AVS contents were strongly correlated with reactive iron and organic carbon (r=0.84; r=0.83 respectively), evidencing their dominant role for AVS formation under semi-arid conditions. On the other hand, the recorded ΣSEM/AVS values remained >1 evidencing a little control of AVS over the bioavailability of trace metals and, thus, its minor role as a sink for toxic metals.