Ecological risk of mercury in bottom sediments and spatial correlation with land use in Neotropical savanna floodplain lakes, Araguaia River, Central Brazil.

The Araguaia River floodplain is an important biogeographic boundary between the two largest South American biomes: the Cerrado (Brazilian Savanna) and the Amazon rainforest. The large-scale degradation due to land use conversion experienced in the Araguaia River watershed represents a potential source of mercury (Hg) transport to aquatic ecosystems. However, more information is needed about the dynamics of Hg distribution in savanna floodplains, including the Araguaia River floodplain. We analyzed total mercury (THg) concentrations in the bottom sediments of 30 lakes connected to the Araguaia River and four tributaries, aiming to evaluate the environment's integrity based on the geoaccumulation index (Igeo) and the ecological risk index (ERI). The principal component analysis was applied to examine associations between Hg concentrations, environmental conditions, and land use intensity among lakes associated with different river systems. We used indicator cokriging to identify areas with a greater probability of Hg pollution and ecological risk associated with land use intensity. The land use data showed the predominance of areas used for pasture in the Araguaia River basin. THg concentrations in the sediments varied between 22.6 and 81.9 ng g-1 (mean: 46.5 ± 17.7 ng g-1). Sediments showed no significant pollution (Igeo: 1.35 - 0.50; Classes 1 and 2) and low to considerable ecological risks (ERI: 23.5-85.1; Classes 1 to 3). THg in bottom sediments was associated with land use, water turbidity and electrical conductivity, and sediment organic matter. The indicator cokriging indicates a moderate to strong spatial dependence between land use intensity and Hg, confirming the contribution of anthropic sources to the increment of ecological risk but also the influence of extrinsic factors (such as environmental conditions, geology, and hydrology). Integrating sediment assessment and land use indices with geostatistical methods proved a valuable tool for identifying priority areas for Hg accumulation at a regional scale.

Spatio-temporal study of water quality variables in the Rio de Ondas Hydrographic Basin, west of Bahia, Brazil using multivariate analysis.

Water bodies are containers that receive a large load of water quality variables through the release of domestic, industrial, and agricultural effluents. With this focus, this work aimed to conduct a temporal-spatial variability study in the Rio de Ondas Hydrographic Basin through multivariate statistical analysis. For this, seventeen collection sites were established in four stations along the Rio de Ondas and its tributaries between 2017 and 2018. Ionic chromatography with suppressed conductivity was used for ions determination, while ICP-OES determined metals' total concentrations. The land use and occupation assessment between 1985 and 2021 was using data from MapBiomas were used and the descriptive and multivariate analysis of the data using version free of the Statistica software. The results showed that, in 30 years, there was a growth of 569% of agricultural activities in the watershed area, with significant suppression of native vegetation, favoring the transport of contaminants to rivers. Ca2+, PO42-, Al, Cu, and Zn concentrations showed a statistically significant difference between the seasons, with higher medians in the rainy season. Rainy season influenced the formation of three groups in the PCA, consisting of electrical conductivity, salinity, TDS, and PO42- (group 1); temperature, Fe, SO42-, and Cl- (group 2); and Ca2+, Mg2+, Na+, and HCO3- (group 3). The strong correlation between parameters of each group indicates anthropic influence on the watershed's water quality. However, levels are within the potability standard.

Mercury spatiality and mobilization in roadside soils adjacent to a savannah ecological reserve.

Mercury (Hg) is a persistent environmental pollutant of global concern. Recognized anthropic contributions to environmental Hg pollution include fuel fossil emissions, soil erosion, and industrial and mining activities. Environmental Hg that enters water bodies can be methylated before entering the food chain and contaminating man and wildlife. We used a kriging approach for sampling and X-ray crystallography to study the pressure of road-traffic Hg emissions on soil Hg concentrations in an ecological reserve (ESECAE) in Central Brazil' savannah. We took samples of organic (n = 144) and mineral (n = 144) layers from the road-side and from the undisturbed soils at 0.1, 1, and 2 km from traffic, inside the ESECAE. Overall, total mercury (THg) concentrations determined by atomic absorption spectrophotometry were significantly higher in the organic layer than in the mineral layer. The mean soil THg in the organic and mineral layers was highest at the roadside (respectively 19.77 ± 12.01 and 16.18 ± 11.54 µg g-1), gradually decreasing with the distance from the road. At 2 km, the mean soil THg was 0.09 ± 0.30 and 0.029 ± 0.03 µg g-1, respectively, for the organic and mineral layers. X-ray crystallography showed mineralogical similarity of the sampled soils, indicating Hg externality, i.e, it did not originate from existing soil minerals. Co-kriging analysis (n = 288) confirmed Hg hotspots on the roadsides and a faster mobilization occurring up to a distance of 1 km for both layers. The soil reception and retention of traffic Hg emissions are mainly in the organic layer and can impact subsoil and adjacent areas. Thus, traffic soil-Hg pollution is limited to the road proximities; THg concentrations are high up to 100 m with an inflection point at 1 km.

Methane emission of Santa Inês sheep fed cottonseed by-products containing different levels of gossypol.

The aim of this study was to evaluate the methane (CH4) emission of Santa Inês sheep fed cottonseed by-products, verifying if the gossypol content of these feedstuffs affects CH4 emission. Twelve late-lactating Santa Inês sheep (44.8 ± 7.5 kg body weight (BW)) were allocated in metabolic cages for an experimental period of 19 days, 14 days for adaptation and 5 days for measuring CH4 emission and dry matter intake (DMI). The animals were divided into four treatments, established in accordance with the cottonseed by-product used in concentrate formulation: Control (CON - no cottonseed by-product), Whole cottonseed (WCS), Cottonseed cake (CSC), and Cottonseed meal (CSM). The free gossypol level of the concentrates were 0, 1,276, 350, and 190 ppm for CON, WCS, CSC, and CSM, respectively. Also, the animals received Cynodon dactylon cv. Coast Cross hay, water, and mineral salt ad libitum. The ether extract content of the diets was balanced between treatments by including soybean oil in concentrates. The technique used to measure the CH4 emission was the sulfur hexafluoride (SF6) tracer technique, and the gas samples collected were quantified by analysis in gas chromatography system. The CH4 emission was evaluated considering the daily emission (g CH4/day); DMI (g CH4/kg DMI); and BW (g CH4/kg BW). No statistical difference was found (P > 0.05) between treatments for DMI and CH4 parameters. In the regression analysis, no significant relation (P > 0.05) between gossypol content and CH4 emission was observed. These results suggest that gossypol does not affect rumen methanogenesis.

Adapted Sequential Extraction Protocol to Study Mercury Speciation in Gold Mining Tailings: Implications for Environmental Contamination in the Amazon.

Artisanal small-scale gold mining (ASGM), an increasingly prevalent activity in South America, generates mercury-contaminated tailings that are often disposed of in the environment, leading to the introduction of mercury into ecosystems and the food web, where it bioaccumulates. Therefore, studying the geochemical processes involved in the desorption and dissolution of mercury in these tailings is essential for critical risk evaluations in the short and long term. For this purpose, sequential extraction procedures (SEPs) can be useful because they help to identify the phases to which Hg is associated, although they also have limitations such as a lack of selectivity and specificity. In this work, we propose a modified four-step SEP: exchangeable mercury (F1), oxidizable mercury (F2), mercury bound to Fe oxides (F3), and strongly bound mercury (F4). To test this adapted sequential extraction method, we evaluated the Hg contamination in mercury-contaminated tailings of the Amazon basin. The results revealed a total mercury concentration of 103 ± 16 mg·kg-1 in the tailings, with a significant portion in F1 (28% of the total), where Hg was bioavailable. The large Hg concentration in F3 (36%) suggested that Fe oxides likely contribute to mercury retention. Together, the SEP results emphasize the urgent need for improved surveillance of gold mining activities and responsible tailings management practices to mitigate environmental contamination and safeguard the health of the Amazon ecosystem.

Pesticides in surface water of the Ondas river watershed, western Bahia, Brazil: Spatial-seasonal distribution and risk assessment.

This study investigated the occurrence and seasonal distribution of different classes of pesticides in surface waters of the Ondas River Watershed, as well as potential risks to the aquatic health and human water consumption in the western region of Bahia state, Brazil. Two gas chromatography-mass spectrometry analytical methods were applied to monitor 34 pesticides in water samples collected during both the dry and rainy seasons at 17 sites. Upon individual analysis, only γ-HCH, methoxychlor, demeton-S, methyl parathion, fenitrothion, chlorpyrifos, and azoxystrobin exhibited statistically significant differences between seasons. During rainy season, concentration medians of residues were higher for γ-HCH (74.7 ng L-1), methoxychlor (25.1 ng L-1), and azoxystrobin (47.2 ng L-1), potentially linked to historical contamination or illegal use. Conversely, pesticides like methyl parathion, fenitrothion, and chlorpyrifos, belonging to the organophosphate class, showed higher concentration medians in the dry period, measuring 75.1, 5.50, and 10.8 ng L-1, respectively, probably due to region crop activities. The risk quotient (RQ) assessment for aquatic life indicated that 59.0% of the samples in the dry season and 76.0% in the rainy season had RQ values greater than one, signifying a critical scenario for species conservation. Regarding human consumption, elevated risks were observed for heptachlor in both sampling periods and for azoxystrobin during the rainy season, surpassing RQ levels above 1, indicating danger in untreated water ingestion. Additionally, 24.0% and 53.0% of the samples in the dry and rainy seasons, respectively, contained at least one pesticide exceeding the EU resolution limit (100 ng L-1). Therefore, considering this information, implementing mitigation measures to avoid the river's contamination becomes imperative.

A voltammetric peptide biosensor for Cu2+ metal ion quantification in coffee seeds.

A prion-derived copper(II)-binding peptide was assembled onto a gold electrode for the building of a voltammetric biosensor for measuring the Cu2+ metal ion in biological samples. The chosen sequence was H-CVNITKQHTVTTTT-NH2, with an appended cysteine residue for binding to the gold surface as a self-assembled monolayer and a histidine residue as the anchorage point for copper(II) complexation. The biosensor showed a linear range of 10-7 to 10-6 M with an 8.0 × 10-8 M detection limit and a 1.0 × 10-7 M quantification limit, with good precision, trueness, and absence of matrix effect. The quantification of Cu2+ was performed in the presence of other transition metal ions, such as Zn2+, Cd2+, Fe2+, or Ni2+, which indicates the excellent selectivity of the biosensor. When the modified electrode was applied for measuring copper(II) in calcined coffee seeds, a difference in copper amount was observed between two Coffea arabica cultivars that were submitted to a treatment with a copper-based antifungal, showing the applicability of the biosensor in the agricultural field.

Mercury Contamination as an Indicator of Fish Species' Trophic Position in the Middle Araguaia River, Brazil.

This study evaluates the use of mercury (Hg) concentrations in fish muscle tissue to determine a species' trophic position (TP) in its environment. A campaign conducted in 2019 along 375 km in the middle Araguaia River basin, Brazil, resulted in 239 organisms from 20 species collected. The highest total mercury (THg) concentrations were found in Pellonacastelnaeana (6.93 µg·g-1, wet weight) and in Triportheus elongatus (3.18 µg·g-1, wet weight), whose TPs were different according to the FishBase database. However, they occupied the same trophic level in this study. The intra-specific comparison showed a difference in Hg concentrations between individuals captured in distinct sites. The study of the biota-sediment accumulation factor (BSAF) showed that spatiality interferes with a species' TP. Statistical analyses revealed that when we used a predicted species' TP based on each individual's size, it explained 72% of the variability in THg concentration across all fish species. Multiple regression analysis confirmed that standard length and FishBase values are positively associated with THg (R2 = 0.943). These results point to Hg as a viable indicator of a fish species' TP since it reflects regional, biological, and environmental factors, as demonstrated here for the middle Araguaia River.

Spatiotemporal evaluation of organochlorine pesticide residues in bottom sediments of the Rio de Ondas hydrographic basin, western Bahia, Brazil.

The Rio de Ondas Hydrographic Basin (ROHB), Bahia state, Brazil, is located in a region with abundant water resources and is highly impacted by intense agricultural activity. In such a scenario, the use of organochlorine pesticides can represent a potential risk to the aquatic environments, due to their persistence, high bioaccumulation capacity, and high toxicity. Thus, organochlorine pesticide residues in bottom sediment samples from rivers on eighteen sites distributed along the ROHB in the dry and rainy periods were analyzed by gas chromatography coupled with mass spectrometry. The validated method showed no matrix effect, recoveries ranging from 82% (ß-HCB) to 118% (DDD), limits of detection between 0.003 ng g-1 (α-HCH) and 0.011 ng g-1 (DDT), limits of quantification of 0.010 ng g-1 (α-HCH) to 0.036 ng g-1 (DDT), repeatability with the highest relative standard deviation of 0.97% (α-hexachlorocyclohexane at 2.000 ng g-1), and inter-day precision ranging from 10% (aldrin at 0.050 ng g-1 and 0.600 ng g-1 and α-endosulfan at 0.600 ng g-1) to 25% (ß-endosulfan at 0.050 ng g-1). Although most compounds were banned since 1985, it was observed that their residues were widely distributed in the ROHB, with the total concentrations varying from 3.242 ng g-1 (P02) to 12.052 ng g-1 (P17) and from 0.313 ng g-1 (P14) to 30.861 ng g-1 (P13) in the dry and rainy periods, respectively, which may be related to historical contamination and/or prohibited use. Moreover, the spatiotemporal variation showed the highest concentrations of organochlorine pesticide residues in the rainy season, coinciding with the planting period.