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

In situ barium phytoremediation in flooded soil using Typha domingensis under different planting densities.

The management of initial planting density can be a strategy to increase barium phytoextraction from soil, reducing the time required for soil decontamination. To delimit the ideal planting density for barium (Ba) phytoremediation using Typha domingensis, we conducted a 300-day experiment in an area accidentally contaminated with barite. Four initial planting densities were tested: 4, 8, 12, and 16 plantsm-2 (D4, D8, D12, and D16 treatments, respectively). Plant development was evaluated periodically, and the phytoextraction efficiency was determined at the end of the trial. The initial planting density affected Ba phytoremediation by T. domingensis monoculture. Phytoextraction potential was better represented by the mass-based translocation factor (mTF) than the concentration-based translocation factor. D16 promoted the highest final number of plants and biomass production, but the mass of Ba in the aerial part did not differ among D8, D12, and D16. D4 resulted in more Ba accumulated belowground than aboveground (6.3 times higher), whereas D12 and D16 achieved the greatest mTFs. Higher absorption of Ba from soil can be achieved using less T. domingensis individuals at the beginning of the treatment (D4 and D8) but with high accumulation in belowground tissues. We conclude that the D8 density is considered the most appropriate if considering the phytoextraction potential and field management facilitated using fewer plants.

Phytoremediation and natural attenuation of sulfentrazone: mineralogy influence of three highly weathered soils.

This study evaluated remediation of the herbicide sulfentrazone in soils with three different mineralogies (kaolinite, hematite, and gibbsite) and three remediation sulfentrazone treatments (Canavalia ensiformis L., Crotalaria juncea L., and natural attenuation). This study was conducted in a factorial scheme, in triplicate with randomized block design. Sulfentrazone was applied at 0 and 400 g ha-1. We analyzed sulfentrazone residue in the soils by high-performance liquid chromatography and confirmed the results with bioassays of Pennisetum glaucum. Herbicide movement was greater in the kaolinitic soil without plant species. The retention of herbicide in the kaolinitic soil occurred in larger quantities in the 0-12 cm layer, with higher levels found in the treatments with plants. In the hematitic soil with C. juncea, all applied herbicides were concentrated in the 0-12 cm layer. In the other hematitic soil treatments, sulfentrazone was not detected by chemical analysis at any soil depth, although in many treatments, it was detected in the bioassay. Phytoremediation was more efficient with C. ensiformis grown in gibbsitic soil, reducing the sulfentrazone load by approximately 27%. Natural attenuation was more efficient than phytoremediation in oxidic soils due to soil pH and texture soils favored microbial degradation of the compound. Highlights The influence of soil mineralogy of herbicide sulfentrazone retention was evaluated. Canavalia ensiformis and Crotalaria juncea were evaluated as phytoremediation plants. Kaolinite soils presented great movement of sulfentrazone in the soil. Natural attenuation is more efficient in oxide soils than phytoremediation.

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.

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.

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.

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.

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.

Effect of planting density of the macrophyte consortium of Typha domingensis and Eleocharis acutangula on phytoremediation of barium from a flooded contaminated soil.

Barite (BaSO4) is a component of drilling fluids used in the oil and gas industry and may cause barium (Ba) contamination if it is spilled onto flooded soils. Under anoxic soil conditions and low redox potential, sulfate can be reduced to a more soluble form (sulfide), and Ba can be made available. To design a solution for such environmental issues, a field study was conducted in a Ba-contaminated flooded area in Brazil, in which we induced Ba phytoextraction from the management of the planting density of two intercropped macrophytes. Typha domingensis and Eleocharis acutangula were grown in four initial planting densities: "Ld" (low density: 4 and 32 plants m-2); "Md" (medium density: 8 and 64 plants m-2); "Hd" (high density: 12 and 128 plants m-2); "Vhd" (very high density: 16 and 256 plants m-2). Vhd produced the largest number of plants after 300 days. However, the treatments did not differ in terms of the amount of biomass. The increments in the initial planting density did not increase the Ba concentration in the aerial part. The greatest Ba phytoextraction (aerial part + root) was achieved by Ld treatment, which removed approximately 3 kg of Ba ha-1. Md and Vhd treatments had the highest Ba translocation factors. Because more plants per area did not result in greater Ba phytoextraction, a lower planting density was recommended for the intercropping of T. domingensis and E. acutangula to promote the phytoextraction of barium, due to possible lower implementation costs in contaminated flooded environments.

Phytoremediation in flooded environments: Dynamics of barium absorption and translocation by Eleocharis acutangula.

Macrophytes are widely used in water treatment and have potential for remediation of flooded soils. Many techniques have been proposed to increase the phytoextraction of metals by macrophytes, however, the knowledge of periods of maximum absorption and translocation is essential and is a gap in the management of phytoremediation. To evaluate the absorption and translocation of Ba over time by Eleocharis acutangula, a greenhouse experiment was conducted and the dry matter production of plants, Ba content in the roots and aerial parts, mass of Ba accumulated in plants, translocation factors and removal coefficients of Ba, and Ba content in two layers of the soil (0.0-0.1 m and 0.1-0.2 m) were determined. The highest translocation rates were observed after 105 days of cultivation, when the plants reached a state of hyperaccumulation. The maximum accumulation of barium occurred in the aerial parts of the plants at 105 days and in the roots at both 120 and 180 days. The barium content was reduced up to 120 days, as a result of an increase in available barium content in the soil layer of 0.0-0.1 m up to 105 days and in the layer 0.10-0.20 m up to 120 days, favoring the intense accumulation of Ba during this period. After 120 days of cultivation, the accumulation in the roots maintained a high coefficient of removal of Ba from the soil to the plant. After 180 days the available barium in the soil was depleted due to this high rate of removal by the roots.

Cutting frequency effect on barium phytoextraction by macrophytes in flooded environment: A field trial.

In anoxic environmental conditions and with a drastic reduction of the redox potential, the barium sulphate used in petroleum drilling fluids becomes a hazard to the ecosystem. A field study was conducted in Brazil in an area with a history of accidental Barium (Ba) contamination to evaluate the role of frequent plant cutting on phytoremediation. The plant species Typha domingensis and Eleocharis acutangula, cultivated in a combined plantation, were subjected to four different cut frequencies: every 90 days (four cuts), 120 days (three cuts), 180 days (two cuts), or 360 days (one cut). The total amount of Ba extracted from the soil by the plants was evaluated for each treatment and at different soil depths Overall, total Ba in the soil decreased the most dramatically for cut frequencies of 120 (37.83%) and 180 (47.73%) days at 0-0.2 m below the surface, and with cut frequencies of 120 (51.98%) and 360 (31.79%) at 0.2-0.4 m depth. Further, total Ba in the plant biomass was greatest in the 120 and 360-days frequency groups. Thus, cuts at intervals of 120 days or more are associated with high levels of Ba in the plant tissue and a decrease of soil Ba.