Rare earth elements (REEs) are generally defined as a homogenous group of elements with similar physical-chemical properties, encompassing Y and Sc and the lanthanides elements series. Natural REEs contents in soils depend on the parent material, the soil genesis processes and can be gradually added to the soil by anthropogenic activities. The REEs have been considered emerging pollutants in several countries, so the establishment of regulatory guidelines is necessary to avoid environmental contamination. In Brazil, REE soils data are restricted to some regions, and knowledge about them in the Amazon soils is scarce, although this biome covers more than 40% of the Brazilian territory. Thus, the objectives of this study were to determine the REE content in soils of two hydrographic basins (Solimões and Rio Negro) of the Amazon biome, establish their Quality Reference Values (QRV) and to investigate the existence of enrichment of REEs in urban soils. The ΣREE(Y + Sc) content of Solimões surface samples was 109.28 mg kg⁻¹ and the ΣREE(Y + Sc) content in the subsurface samples was 94.11 mg kg⁻¹. In soils of Rio Negro basin, the ΣREE(Y + Sc) was 43.95 15 mg kg⁻¹ surface samples and 38.40 mg kg⁻¹ in subsurface samples. The ΣREE(Y + Sc) in urban topsoils samples was 38.62 mg kg⁻¹. The REEs contents pattern in three studied areas are influenced in different amplitude by natural soil properties. The REEs content in urban topsoils were slightly higher than the Rio Negro pristine soils, but the ecological risk was low. QRVs recommend for Solimões soils ranged from 0.01 (Lu) to 145.6 mg kg⁻¹ (Ce) and for Rio Negro soils ranged from 0.05 (Lu) to 15.8 mg kg⁻¹ (Ce).

It is widely recognized that apex predators, such as large sharks with highly migratory behavior, are particularly vulnerable to pollution, mainly due to biomagnification processes. However, in highly impacted areas, mesopredator sharks with resident behavior can be as vulnerable as apex sharks. In this context, this study evaluated cadmium (Cd), mercury (Hg), lead (Pb), and rubidium (Rb) concentrations, as well as the potentially protective effects of selenium (Se) and the behavior of two non-enzymatic biomarkers, metallothionein (MT) and reduced glutathione (GSH), employing the Atlantic nurse shark Ginglymostoma cirratum as a study model and compared the results with other resident benthic sharks, as well as highly mobile apex sharks. Muscle tissue samples from 28 nurse sharks opportunistically sampled from the Brazilian Amazon Coast were analyzed. Lower metal concentrations were observed for Pb, Rb and Se in the rainy season, while statistically significant correlations between metals were observed only between Hg and Cd and Pb and Se. Molar ratio calculations indicate potential protective Se effects against Pb, but not against Cd and Hg. No associations between MT and the determined metals were observed, indicating a lack of detoxification processes via the MT detoxification route. The same was noted for GSH, indicating no induction of this primary cellular antioxidant defense. Our results indicate that benthic/mesopredator sharks with resident behavior are, in fact, as impacted as highly mobile apex predators, with the traditional detoxification pathways seemingly inefficient for the investigated species. Moreover, considering the studied population and other literature data, pollution should be listed as a threat to the species in future risk assessments.

Sewage pollution is a principal factor of decreasing water quality, although it has not been considered a real impact in Amazonia that is still considered a pristine environment around the world. Thus, this study aimed to assess the levels of sewage contamination in sediments from three streams crossing Manaus − a Brazilian city of 2,403,796 inhabitants in the heart of the Amazon rain forest. Cholesterol, cholestanol, brassicasterol, ergosterol, stigmasterol, β-sitosterol, campesterol, stigmastanol, coprostanol, and epicoprostanol levels were determined by liquid chromatography tandem mass spectrometry (LC−MS/MS). The fecal indicator, coprostanol, was found in high concentrations (509−12 830 ng g⁻¹) and high relative proportions (21–54%) in all samples collected in the Mindu stream that crosses many heavily populated districts of the city, and in the Quarenta stream that crosses the Industrial District of Manaus. The sediments of the Tarumã-Açu stream also presented coprostanol; however, concentrations (<LOQ−142 ng g⁻¹) and relative proportions (0–7%) were much lower in this stream. Sterol ratios indicate a severe contamination of the urban streams (Mindu and Quarenta) and a low to moderate contamination of the partially urban stream (Tarumã-Açu). This is the first study evaluating the levels of sewage contamination of Amazon streams using sterol biomarkers and the results obtained herein indicate the need of an immediate implementation of effective sewage treatment strategies. Additionally, these findings may be considered as baseline concentrations for future monitoring programs of that globally important environment.

Even though the Amazon region is widely studied, there is still a gap regarding Cr exposure and its risk to human health. The objectives of this study were to 1) determine Cr concentrations in seven chemical fractions and 6 particle sizes in Amazon soils, 2) quantify hexavalent Cr (CrVI) concentrations using an alkaline extraction, 3) determine the oral and lung bioaccessible Cr, and 4) assess Cr exposure risks based on total and bioaccessible Cr in soils. The total Cr in both A (0–20 cm) and B (80–100 cm) horizons was high at 2346 and 1864 mg kg⁻¹. However, sequential extraction indicated that available Cr fraction was low compared to total Cr, with Cr in the residual fraction being the highest (74–76%). There was little difference in total Cr concentrations among particle sizes. Hexavalent Cr concentration was also low, averaging 0.72 and 2.05 mg kg⁻¹ in A and B horizon. In addition, both gastrointestinal (21–22 mg kg⁻¹) and lung (0.95–1.25 mg kg⁻¹) bioaccessible Cr were low (<1.2%). The low bioavailability of soil Cr and its uniform distribution in different particle sizes indicated that Cr was probably of geogenic origin. Exposure based on total Cr resulted in daily intake > the oral reference dose for children, but not when using CrVI or bioaccessible Cr. The data indicated that it is important to consider both Cr speciation and bioaccessibility when evaluating risk from Cr in Amazon soils.

Emissions from burning of biomass in the Amazon region have adverse effects on the environment and human health. Herein, particulate matter (PM) emitted from biomass burning in the Amazon region during two different periods, namely intense and moderate, was investigated. This study focused on: i) organic characterization of nitro- and oxy-polycyclic aromatic hydrocarbons (PAHs); ii) assessment of the excess lifetime cancer risk (LCR); and iii) assessment of the in vitro mutagenic effects of extractable organic matter (EOM). Further, we compared the sensitivity of two mutagenicity tests: Salmonella/microsome test and cytokinesis-block micronucleus (CBMN) with human lung cells. Among the nitro-PAHs, 2-nitrofluoranthene, 7-nitrobenz[a]anthracene, 1-nitropyrene, and 3-nitrofluoranthene showed the highest concentrations, while among oxy-PAHs, 2-metylanthraquinone, benz[a]anthracene-7,12-dione, and 9,10-anthraquinone were the most abundant. The LCR calculated for nitro-PAH exposure during intense biomass burning period showed a major contribution of 6-nitrochrysene to human carcinogenic risk. The EOM from intense period was more mutagenic than that from moderate period for both TA98 and YG1041 Salmonella strains. The number of revertants for YG1041 was 5–50% higher than that for TA98, and the most intense responses were obtained in the absence of metabolic activation, suggesting that nitroaromatic compounds with direct-acting frameshift mutagenic activity are contributing to the DNA damage. Treatment of cells with non-cytotoxic doses of EOM resulted in an increase in micronuclei frequencies. The minimal effective dose showed that Salmonella/microsome test was considerably more sensitive in comparison with CBMN mainly for the intense burning period samples. This was the first study to assess the mutagenicity of EOM associated with PM collected in the Amazon region using Salmonella/microsome test. The presence of compounds with mutagenic effects, particularly nitro- and oxy-PAHs, and LCR values in the range of 10⁻⁵ indicate that the population is potentially exposed to an increased risk of DNA damage, mutation, and cancer.

There is an ongoing debate on the fate of mercury (Hg) in areas affected by artisanal and small-scale gold mining (ASGM). Over the last 30 years, ASGM has released 69 tons of Hg into the southeastern Peruvian Amazon. To investigate the role of suspended matter and hydrological factors on the fate of ASGM-Hg, we analysed riverbank sediments and suspended matter along the partially ASGM-affected Malinowski-Tambopata river system and examined Hg accumulation in fish. In addition, local impacts of atmospheric Hg emissions on aquatic systems were assessed by analysing a sediment core from an oxbow lake. Hg concentrations in riverbank sediments are lower (20–53 ng g−1) than in suspended matter (∼400–4000 ng g−1) due to differences in particle size. Elevated Hg concentrations in suspended matter from ASGM-affected river sections (∼1400 vs. ∼30–120 ng L−1 in unaffected sections) are mainly driven by the increased amount of suspended matter rather than increased Hg concentrations in the suspended matter. The oxbow lake sediment record shows low Hg concentrations (64–86 ng g−1) without evidence of any ASGM-related increase in atmospheric Hg input. Hg flux variations are mostly an effect of variations in sediment accumulation rates. Moreover, only 5% of the analysed fish (only piscivores) exceed WHO recommendations for human consumption (500 ng g−1). Our findings show that ASGM-affected river sections in the Malinowski-Tambopata system do not exhibit increased Hg accumulation, indicating that the released Hg is either retained at the spill site or transported to areas farther away from the ASGM areas. We suspect that the fate of ASGM-Hg in such tropical rivers is mainly linked to transport associated with the suspended matter, especially during high water situations. We assume that our findings are typical for ASGM-affected areas in tropical regions and could explain why aquatic systems in such ASGM regions often show comparatively modest enrichment in Hg levels.

Pollution by plastics is a global problem, in particular through the contamination of aquatic environments and biodiversity. Although plastic contamination is well documented in the aquatic fauna of the oceans and large rivers of the world, there are few data on the organisms of headwater streams, especially in tropical regions. In the present study, we evaluated the contamination of small fish by plastics in Amazonian streams. For this, we evaluated the shape and size, and the abundance of plastics in the gastrointestinal tracts and gills of 14 fish species from 12 streams in eastern Brazilian Amazon. We used a Generalized Linear Mixed Model (GLMM) to compare the levels of contamination among species and between organs. Only one individual of the 68 evaluated (a small catfish Mastiglanis cf. asopos) contained no plastic particles, and no difference was found in the contamination of the gills and digestive tract. However, Hemigrammus unilineatus presented less contamination of both the gills and the digestive tract than the other species, while Polycentrus schomburgkii had less plastic in the gastrointestinal tract, whereas Crenicichla regani and Pimelodella gerii both had a larger quantity of plastic adhered to their gills in comparison with the other species. Nanoplastics and microplastics adhered most to the gills, while plastic fibers were the most common type of material overall. This is the first study to analyze plastic contamination in fish from Amazonian streams, and in addition to revealing high levels of contamination, some species were shown to possibly be more susceptible than others. This reinforces the need for further, more systematic research into the biological and behavioral factors that may contribute to the greater vulnerability of some fish species to contamination by plastics.Amazonian stream fish show contamination by plastics. The species respond differently. The smaller the particle, the easier it is to adhere to the gills.

The rate of deforestation in Brazil increased by 29% between 2015 and 2016, resulting in an increase of greenhouse gas emissions (GHG) of 9%. Deforestation fires in the Amazonia are the main source of GHG in Brazil. In this work, amounts of CO2, CO, main hydrocarbon gases and PM2.5 emitted during deforestation fires, under real conditions directly in Brazilian Amazonia, were determined. A brief discussion of the relationship between the annual emission of CO2 equivalent (CO2,eq) and Paris Agreement was conducted. Experimental fires were carried out in Western Amazonia (Candeias do Jamari, Rio Branco and Cruzeiro do Sul) and results were compared with a previous fire carried out in Eastern Amazonia (Alta Floresta). The average total fresh biomass on the ground before burning and the total biomass consumption were estimated to be 591 ton ha−1 and 33%, respectively. CO2, CO, CH4, and non–methane hydrocarbon (NMHC) average emission factors, for the four sites, were 1568, 140, 8, and 3 g kg−1 of burned dry biomass, respectively. PM2.5 showed large variation among the sites (0.9–16 g kg−1). Emissions per hectare of forest were estimated as 216,696 kg of CO2, 18,979 kg of CO, 1,058 kg of CH4, and 496 kg of NMHC. The average annual emission of equivalent CO2 was estimated as 301 ± 53 Mt year−1 for the Brazilian Amazonia forest. From 2013, the estimated CO2,eq showed a trend to increase in Amazon region. The present study is an alert and provides important information that can be used in the development of the public policies to control emissions and deforestation in the Brazilian Amazonia.

Cacao from South America is especially used to produce premium quality chocolate. Although the European Food Safety Authority has not established a limit for cadmium (Cd) in chocolate raw material, recent studies demonstrate that Cd concentrations in cacao beans can reach levels higher than the legal limits for dark chocolate (0.8 mg kg−1, effective January 1st, 2019). Despite the fact that the presence of Cd in agricultural soils is related to contamination by fertilizers, other potential sources must be considered in Ecuador. This field study was conducted to investigate Cd content in soils and cacao cultivated on Ecuadorian farms in areas impacted by oil activities. Soils, cacao leaves, and pod husks were collected from 31 farms in the northern Amazon and Pacific coastal regions exposed to oil production and refining and compared to two control areas. Human gastric bioaccessibility was determined in raw cacao beans and cacao liquor samples in order to assess potential health risks involved. Our results show that topsoils (0–20 cm) have higher Cd concentrations than deeper layers, exceeding the Ecuadorian legislation limit in 39% of the sampling sites. Cacao leaves accumulate more Cd than pod husks or beans but, nevertheless, 50% of the sampled beans have Cd contents above 0.8 mg kg−1. Root-to-cacao transfer seems to be the main pathway of Cd uptake, which is not only regulated by physico-chemical soil properties but also agricultural practices. Additionally, natural Cd enrichment by volcanic inputs must not be neglected. Finally, Cd in cacao trees cannot be considered as a tracer of oil activities. Assuming that total Cd content and its bioaccessible fraction (up to 90%) in cacao beans and liquor is directly linked to those in chocolate, the health risk associated with Cd exposure varies from low to moderate.

Oil extraction activities in the Northern Peruvian Amazon have generated a long-standing socio-environmental conflict between oil companies, governmental authorities and indigenous communities, partly derived from the discharge of produced waters containing high amounts of heavy metals and hydrocarbons. To assess the impact of produced waters discharges we conducted a meta-analysis of 2951 river water and 652 produced water chemical analyses from governmental institutions and oil companies reports, collected in four Amazonian river basins (Marañon, Tigre, Corrientes and Pastaza) and their tributaries. Produced water discharges had much higher concentrations of chloride, barium, cadmium and lead than are typically found in fresh waters, resulting in the widespread contamination of the natural water courses. A significant number of water samples had levels of cadmium, barium, hexavalent chromium and lead that did not meet Peruvian and international water standards. Our study shows that spillage of produced water in Peruvian Amazon rivers placed at risk indigenous population and wildlife during several decades. Furthermore, the impact of such activities in the headwaters of the Amazon extended well beyond the boundaries of oil concessions and national borders, which should be taken into consideration when evaluating large scale anthropogenic impacts in the Amazon.