Comparative analysis of sediment quality indices using different reference values in an environmental protection area in Southeastern Brazil.

Contamination of aquatic ecosystems by potentially toxic elements (PTEs) is a concerning environmental issue, given their persistence, toxicity potential, and ability to accumulate in living organisms. Several studies have been conducted to assess the contamination of aquatic ecosystems by PTEs, using pollution and ecological risk indices that rely on the concentration of these elements in aquatic sediments. However, many of these studies use global reference values for calculating the indices, which can lead to misleading interpretations due to substantial variations in PTEs concentrations influenced by the geological characteristics of each region. Therefore, the use of regional reference values is more appropriate when available. This study aimed to investigate variations in the results of five indices, employing global, regional, and quality reference values, based on sediment samples collected from rivers in the Ipanema National Forest, a protected area in Brazil exposed to various anthropogenic pressures. The results revealed that elements such as Al, Fe, and Mn exceeded the limits allowed by legislation in water samples, while As and Cr surpassed the limits in sediment samples. Comparative analysis highlighted significant discrepancies in the results of the indices when global reference values were used compared to regional and quality reference values, especially for As and Ba. Thus, this study underscores the importance of establishing specific regional values for an accurate assessment of sediment quality and the risks associated with contamination by PTEs in different regions worldwide.

Urban river recovery: a systematic review on the effectiveness of water clean-up programs.

Urban rivers are affected at different levels by the intensification of human activities, representing a serious threat to the maintenance of terrestrial life and sustainable urban development. Consequently, great efforts have been dedicated to the ecological restoration of urban rivers around the world, as a solution to recovering the environmental functionality of these environments. In this sense, the present work aimed to investigate the effectiveness of interventions carried out aimed at the recovery of urban rivers, through a systematic review of the literature between 2010 and 2022, using the search term "rivers recovery." The results showed that there have been notable advances in the implementation of river recovery programs in urban areas around the world between the years analyzed. The ecosystems studied were affected, for the most part, by the increase in the supply of nutrients from domestic and industrial effluents, in addition to having highly urbanized surroundings and with several changes in land use patterns. The preparation of this literature review made it possible to demonstrate that the effectiveness of river recovery is extremely complex, since river recovery projects are developed for different reasons, as well as being carried out in different ways according to the intended objective.

Investigation on humic substance and tetracycline interaction mechanism: biophysical and theoretical studies and assessing their effect on biological activity.

Tetracycline (TC) is a widely used antibiotic, and evaluating its interaction with humic substances (HS) that act as a complexing agent in the environment is essential to understanding the availability of this contaminant in the environment. This study evaluated the interaction between HS and TC using different spectroscopic techniques, theoretical studies, and biological assays simulating environmental conditions. TC interacts with HS, preferably by electrostatic forces, with a binding constant of 9.2 × 103 M-1 (30 °C). This process induces conformational changes in the superstructure, preferably in the HS, like protein fraction. Besides, studies using the 8-anilino-1-naphthalene sulfonate (ANS) probe indicated that the antibiotic alters the hydrophobicity degree on HS's surface. Synchronized fluorescence shows that the TC interaction occurs preferentially with the protein-like fraction of soil organic matter (KSV = 26.28 ± 1.03 M-1). The TC epitope was evaluated by 1H NMR and varied according to the pH (4.8 and 9.0) of the medium, as well as the main forces responsible for the stabilization of the HS-TC complex. The molecular docking studies showed that the formation of the HS-TC complex is carried out spontaneously (ΔG = -7.1 kcal mol-1) and is stabilized by hydrogen bonds and electrostatic interactions, as observed in the experimental spectroscopic results. Finally, biological assays indicated that HS influenced the antimicrobial activity of TC. Thus, this study contributed to understanding the dynamics and distribution of TC in the environment and HS's potential in the remediation of antibiotics of this class in natural systems, as these can have adverse effects on ecosystems and human health.

Interaction between roxarsone, an organic arsenic compound, with humic substances in the soil simulating environmental conditions.

In environmental systems, the soil is a principal route of contamination by various potentially toxic species. Roxarsone (RX) is an arsenic (V) organic compound used to treat parasitic diseases and as an additive for animal fattening. When the animal excretes RX, the residues may lead to environmental contamination. Due to their physicochemical properties, the soil's humic substances (HS) are important in species distribution in the environment and are involved in various specific interaction/adsorption processes. Since RX, an arsenic (V) compound, is considered an emerging contaminant, its interaction with HS was evaluated in simulated environmental conditions. The HS-RX interaction was analyzed by monitoring intrinsic HS fluorescence intensity variations caused by complexation with RX, forming non-fluorescent supramolecular complexes that yielded a binding constant Kb (on the order of 103). The HS-RX interaction occurred through static quenching due to complex formation in the ground state, which was confirmed by spectrophotometry. The process was spontaneous (ΔG < 0), and the predominant interaction forces were van der Waals and hydrogen bonding (ΔH < 0 and ΔS < 0), with an electrostatic component evidenced by the influence of ionic strength in the interaction process. Structural changes in the HS were verified by synchronized and 3D fluorescence, with higher variation in the region referring to the protein-like fraction. In addition, metal ions (except ions Cu(II)) favored HS-RX interaction. When interacting with HS, the RX epitope was suggested by 1H NMR, which indicated that the entire molecule interacts with the superstructure. An enzyme inhibition assay verified the ability to reduce the alkaline phosphatase activity of free and complexed RX (RX-HS). Finally, this work revealed the main parameters associated with HS and RX interaction in simulated environmental conditions, thus, providing data that may help our understanding of the dynamics of organic arsenic-influenced soils.

Leafy vegetables marketed as organic and conventional: assessment of essential and non-essential elements' content.

Trace and potentially toxic elements represent one class of food contaminants that has stimulated research. In markets, two main methods of growing vegetables are generally available: conventional and organic. Conventional farming has been the target of some concerns about the use of agrochemicals, especially the excessive use of pesticides, whereas organic agriculture minimizes the use of agrochemicals. As the main route for potentially toxic elements' absorption by humans is by food intake, it is important to evaluate if the method of cultivation influences their concentrations. This study evaluated the levels of potentially toxic elements and nutrients on four leafy vegetables: curly lettuce, collard greens, escarole, and rocket, cultivated by conventional and organic farming. We found that Al, Ba, Fe, and Sr levels were higher in conventional samples, whereas K, Pb, and Zn were higher in organic. Amongst the elements analysed, values of Fe, Al, and K were around 0.2, 0.3, and 70 g kg-1, respectively, except in collard greens, in which the values were lower. On the other hand, Ba, Sr, and Mn presented higher concentration in collard greens compared to the other vegetables in conventional cultivation (~ 35, 80, and 120 mg kg-1, respectively). The principal component analysis result shows that the samples were grouped according to the type of vegetable, regardless of the type of cultivation. Despite this, the evaluation of the cultivation by different types of farming is important in order to choose the healthiest option.

Natural and anthropogenic sources of potentially toxic elements to aquatic environment: a systematic literature review.

Potentially toxic elements (PTEs) constitute a class of metals, semimetals, and non-metals that are of concern due to their persistence, toxicity, bioaccumulation, and biomagnification in high concentrations, posing risks to the ecosystem and to human health. A systematic literature review (SLR) was used in this study to identify natural and anthropogenic sources of PTEs for the aquatic environment. The databases consulted were ScienceDirect, Scopus, and Web of Science, in the period 2000-2020, using specific terms and filters. After analyzing the titles, abstracts, and full texts, 79 articles were selected for the SLR, in which 15 sources and 16 PTEs were identified. The main anthropogenic sources identified were mining, agriculture, industries, and domestic effluents, and the main natural sources identified were weathering of rocks and geogenic origin. Some places where environmental remediation studies can be carried out were highlighted such as Guangdong province, in China, presenting values of Cd, Cr, and Cu exceeding the national legislation from drinking water and soil quality, and Ardabil Province, in Iran, presenting values of As, Cr, Cu, Ni, Zn, and Pb exceeding the standard for freshwater sediments of USEPA, among others places. With the results exposed in this work, the government and the competent bodies of each locality will be able to develop strategies and public policies aimed at the main sources and places of contamination, in order to prevent and remedy the pollution of aquatic environments by potentially toxic elements.

The environmental importance of iron speciation in soils: evaluation of classic methodologies.

Iron is an essential mineral and one of the most abundant in soils, presenting itself in the environment as ferrous and ferric ions. As each oxidation state of iron has a different role in the environment, its speciation in environmental studies is important. The determination of ferrous iron received great attention from soil chemists because of its important role in agriculture, in redox processes, and as an electron acceptor in the catalysis of organic matter. Methodologies with the use of colorimetric reagents to determine ferrous iron are divergent and not very clear. In this study, we compared two colorimetric reagents (1,10-phenanthroline and ferrozine) to determine the total concentration of iron, ferrous and ferric ions in soil, using simple and low-cost methodologies. The determination of ferrous and total iron with 1,10-phenanthroline colorimetric reagent, following published instructions, did not correlate with ferrozine method, presenting an erroneous quantification. After neutralizing the extract of 1,10-phenanthroline with NaOH, both colorimetric methods allowed to quantify with precision and high yield the amount of ferrous and total iron extracted from the soil. The oxidation states of iron have a different contribution and importance to the environment. In this sense, the improvement of a widely used methodology is crucial for the better study of iron speciation in soil.

Spatial modeling applied to environmental monitoring: identifying sources of potentially toxic metals in aquatic system.

Aquatic contamination by potentially toxic metals is a problem that has been aggravated, especially due to the quantity and the diversity of sources. Locating these sources is not always an easy task, especially because of the wide variety of possibilities. In this context, the application of geostatistical methods may represent an excellent tool to find out sources of metal contaminants in aquatic systems. Thus, the objective of this work was to elaborate an approach to identify sources of potentially toxic metals (Zn, Ba, Pb, Cr, Mn and Fe), by relating their spatial-temporal variations with the local land use patterns, along a longitudinal profile of the Pirapora River, located in the State of Sao Paulo, Brazil. For this purpose, water samples were collected at different points, taking into consideration each specific land use pattern and quantifying the metals contents by microwave plasma atomic emission spectrometry. In this work, thirteen land use patterns have been identified: mining, forestry, abandoned pasture, water, urban area, human occupation, floodplain, bare soil, temporary crop, roads, forest, streets and pasture. The results revealed temporal variations for the metals Ba, Cr, Fe, and Pb and spatial for Zn and Mn, making possible to correlate the presence of these two latter metals with mining and forestry, the most proeminent activities in the region. Overall, this work proposes a model which brings together geoprocessing and analytical methods, in order to correlate spatial-temporal variations of potentially toxic metals with specific land use patterns of a determined region, aiming the environmental monitoring.

Natural organic matter residue as a low cost adsorbent for aluminum.

The contamination of aquatic and terrestrial environments by potentially toxic metals is highlighted by the possible impacts that their high availability can have on the environment. Thus, the development of alternative absorbents that can be used in the remediation of contaminated areas is of great environmental interest. Humin, one of the fractions of natural organic matter, is a promising alternative in studies on the retention of different metals that are environmentally toxic. In this study, the influence of the organic and inorganic humin constituents that are involved in the retention of aluminum species was evaluated. After extraction and calcination to obtain the ashes (inorganic constituents), humin and ash samples were structurally characterized by Fourier transform infrared spectroscopy and scanning electron microscopy. Interaction studies between aluminum-humin and ash-humin were performed in the pH range of 4.0-8.0 and with various contact times. The results of the characterization of humin and ash showed different functional groups present in the structures of these materials. Based on the results of the interaction between humin-aluminum and ash-aluminum, it can be inferred that both the organic and inorganic components of humin are efficient at absorbing aluminum. However, the adsorption isotherms showed that humin and the ashes have different adsorption behaviors. Humin is the only fraction of natural organic matter with a significant inorganic constituent content; it is the fraction least used by researchers in this field and is often discarded as waste. In light of this, the results obtained in this work highlight the importance of humin as a natural adsorbent material. Humin may be promising for the removal of aluminum species in contaminated environments due to the presence of organic and inorganic constituents.

The use of sugar and alcohol industry waste in the adsorption of potentially toxic metals.

One of the waste products of the industrial process of the sugar and alcohol agribusiness is filter cake (FC). This waste product has high levels of organic matter, mainly proteins and lipids, and is rich in calcium, nitrogen, potassium and phosphorous. In this work we characterized samples of FC from sugar and alcohol industries located in sugarcane-producing regions in Brazil and assessed the adsorption of potentially toxic metals (Cu(II), Cd(II), Pb(II), Ni(II) and Cr(III)) by this waste in mono- and multi-elemental systems, seeking to use FC as an adsorbent in contaminated environments. The characterization of FCs showed significant differences between the samples and the adsorption studies showed retention of over 90% of potentially toxic metals. In a competitive environment (multi-metallic solution), the FC was effective in adsorbing all metals except lead, but less effective compared to the mono-metallic solution. These results show the potential for use of this residue as an adsorbent in contaminated environments.

Peat humic substances enriched with nutrients for agricultural applications: competition between nutrients and non-essential metals present in tropical soils.

Improved agricultural productivity, and reduction of environmental impacts, require studies of the interactions between different soil components. Fertilizers marketed as "organic" or "natural", such as peats or humic substances (HS) extracted from peats, are enriched with macro and micronutrients that, according to the manufacturers, are released to the plant in accordance with its needs. This work investigates the complexation capacity of HS for macro and micronutrient metal species, considering the competition, for HS complexation sites, between non-essential metals (aluminium and lead), present in the soil, and the nutrients. Humic substances were found to possess strong affinities for Pb(II) and Al(III), forming stable complexes, with concomitant release of complexed nutrients. Although HS are already used commercially as organic fertilizers, further studies of methods of HS enrichment, aimed at avoiding losses, are highly desirable from environmental and economic perspectives.