Properties and environmental quality of the overburden and tailings of manganese mining in the Eastern Amazon.

Knowledge about the characteristics of overburden and tailings from manganese (Mn) mining is essential for defining their levels of potentially toxic elements (PTEs) and appropriate environmental management. This study aimed to assess the total and bioavailable contents of PTEs in Mn mining areas in the Eastern Amazon, as well as the associated environmental risks. The samples were collected in areas of overburden and tailings deposition, in addition to forest soils in the Azul mine, Carajás Mineral Province, Brazil. These samples were characterized in terms of fertility, granulometry, and total and bioavailable PTE contents. The pH values of the forest soil were more acidic than those of the overburden and tailings, and the organic matter contents were considerably higher in the forest soil. All PTEs, especially Mn, Ba, Cu, Zn, and Pb, presented higher contents in the overburden and tailings. However, chemical fractionation revealed that PTEs were predominantly in the residual fraction, with percentage contents above 60% of the total content. These results suggest a low risk of environmental contamination. The findings of this study may support more efficient environmental rehabilitation in Mn mining areas in the Amazon.

Assessment of the reproduction of six collembolan species in tropical soils naturally rich in potentially toxic elements.

Laboratory ecotoxicological tests are important tools for the management of environmental changes derived from anthropogenic activities. Folsomia candida is usually the model species used in some procedures. However, this species may not be sufficiently representative of the sensitivity of the other collembolan species. This study aimed to evaluate (i) the effects of soils naturally rich in potentially toxic elements (PTE) and soil characteristics on the reproduction and survival of different collembolan species, (ii) whether the habitat function of these soils is compromised, and (iii) to what extent F. candida is representative of the other collembolan species. For this, reproduction tests with six collembolan species were conducted in 14 different samples of soils. In general, collembolan reproduction was not completely inhibited in none of the natural tested soils. Even soils with high pollution load index values did not negatively affect collembolan reproduction for most of the species. In contrast, the lowest collembolan reproduction rates were found in a visually dense soil (lowest volume/weight ratio), highlighting that soil attributes other than total PTE concentration also interfere in the reproduction of collembolans. Our results support the idea that the F. candida species might not be representative of other collembolan species and that laboratory tests to assess soil contaminations should be conducted using diverse collembolan species.

Historical Hg accumulation (∼65 cal kyr BP) in upland lakes of the Southeastern Brazilian Amazonia: New evidence of the extent of geogenic and diagenetic control.

The historical upland lake sediments in the Brazilian Amazon witnessed significant enrichment of total mercury (Hg). However, its spatio-temporal relationships between lakes and the main factors responsible for this enrichment are still poorly constrained. Given this, we geochemically investigated 12 radiometrically dated (extending back to ∼65 cal kyr BP) sediment cores from the Carajás plateau, Brazil. The Hg level in historical sediments presented a large temporal variability (from 1 to 3200 µg/kg), with maximum accumulation peaks observed between 30 and 45 cal kyr BP in core R2, LB3, and R1. However, the lack of the Hg peak in other cores (LV2 and LTI3) during the same period despite being proximity and non-correlation of these Hg peaks with the onset of major volcanic events indicates that this source has little bearing. Hg enrichment is highly dependent on the type of sedimentary facies, with higher values were associated with detritic facies (MI) and detritic+organic facies (P/M). Principal component analysis shows that aluminosilicate minerals and organic matter are essential hosts of Hg in sediments. The positive correlation between Al, Ti, and Hg in detritic facies and their strong coherence with Hg/TOC in R1, R5, LSL, ST02, and LB3 cores indicate that Hg is primarily of lithogenic origin. This can be substantiated by the higher background threshold value of Hg (574 µg/kg) in historical lake sediments compared to those in recent lake sediments (340 µg/kg). However, the most pronounced Hg peak (3200 µg/kg) in R2 around 45 cal kyr BP, which correlates positively with TOC, S, Se, As, and Mo indicates their diagenetic enrichment in organic-rich sediments under anoxic conditions. Thus, in addition to the lithogenic effect, it can be argued that diagenesis can play a significant role in prompting Hg enrichment in the Carajás lake sediments in Amazonia.

Mercury in multimedia system of Itacaiúnas Basin, Brazilian Amazon: An integrated approach to understand its distribution, origin, and ecological risk.

This study presents the first integrated study on total Hg (THg) level in surface soil (SS), bottom soil (BS), stream sediments (SD), lake sediments (LS), stream water (SW), and lake water (LW) of Itacaiúnas River Watershed (IRW), Brazil to investigate the source and distribution of Hg in different environmental media considering contrasts of geological domains and sub-basins and its potential ecological and human risk. Hg content in most of the soils and sediments were above the upper crustal average values (56 µg/kg), however, when compared to the legal limits set by the Resolution CONAMA (Conselho Nacional de Meio Ambiente: soil 500 µg/kg; sediment 486 µg/kg), only 1 soil sample from Parauapebas sub-basin and 4 sediment samples from Violão Lake exceeded the limit. None of the SW and LW samples (<0.2 µg/L; CONAMA limit for Class II freshwater) are markedly contaminated by Hg. The SS and BS show similar contents and spatial distribution of Hg with higher contents being registered mostly in the Itacaiúnas and Parauapebas sub-basins, which are closely correlated with SD. This suggests that Hg levels are largely of geogenic origin and anthropogenic effect is highly limited. Principal Component Analysis (PCA) results show that Hg is strongly associated with total organic carbon (TOC), loss on ignition (LOI), and SO3, indicating organic matter as the main factor controlling the distribution of Hg and this is the major cause of accentuated Hg enrichment in lake sediments. The ecological risk index revealed a low pollution risk for most of the solid samples, except 11% LS and <1.5% SS and SD samples, which registered moderate risk. Health risk assessment indicated no adverse non-carcinogenic health effect on either adults and children in terms of Hg contamination. This information will be useful for Hg risk assessment in the Carajás region and future environmental research in this direction in the Amazonia.

Soil-sediment linkage and trace element contamination in forested/deforested areas of the Itacaiúnas River Watershed, Brazil: To what extent land-use change plays a role?

Trace elements (TE) contamination in forested areas of the Itacaiúnas River Watershed (IRW), Brazilian Amazon, arouses growing interest owing to the rapid deforestation and mining activities. In this study, soils (surface, SS; bottom, BS) and stream sediments (SD) from forested/deforested areas of IRW were analyzed with the aim of (1) evaluating the major sources of TE (mainly As, Ba, Cd, Cu, Co, Cr, Hg, Mo, Mn, Ni, Pb, V, and Zn), and (2) examining the soil-sediment TE link related to land-use change and/or geologic factors. Compositional data analysis (CoDA) was used to eliminate data closure issues and the centred log-ratio (clr) transformation yielded better results in Principal Component Analysis (PCA). The TE distribution pattern was significantly different (p < 0.05) between forested and deforested areas, but in both areas the TE distribution pattern is significantly correlated between SS, BS, and SD, indicating a strong lithogenic control. PCA (clr-transformed) identified the major geochemical bedrock signature as Fe-Ti-V-Cu-Cr-Ni, which is nearly similar in soil and sediments. The more accentuated enrichment and the maximum number of anomalies of these elements were found in the Carajás Basin and are highly coincident with mineral deposits/local lithologies without clear indication of anthropogenic contamination from point sources. Besides geogenic factors, deforestation is also affecting TE distribution in the basin. In deforested areas, Mn was significantly enriched in the surface horizon. Furthermore, linear regression analysis shows stronger TE relationships between soils and sediments in deforested areas than in forested ones, reflecting higher erosion in the former. This could be the reason for the relatively higher enrichment of TE (e.g., Fe, Mn, Cu, Cr, Ni) in deforested sediments. The TE contamination using regional background values provides more accurate results than worldwide reference values. Thus, the former should be considered for a more realistic environmental risk assessment in IRW and other forest ecosystems in the Brazilian Amazon.

Copper mining in the eastern Amazon: an environmental perspective on potentially toxic elements.

Mining activity is of great economic and social importance; however, volumes of metallic ore tailings rich in potentially toxic elements (PTEs) may be produced. In this context, managing this environmental liability and assessing soil quality in areas close to mining activities are fundamental. This study aimed to compare the concentrations of PTEs-arsenic (As), barium (Ba), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), molybdenum (Mo), nickel (Ni), lead (Pb) and zinc (Zn)-as well as the fertility and texture of Cu tailings and soils of native, urban and pasture areas surrounding a Cu mining complex in the eastern Amazon. The levels of PTEs were compared with soil prevention values, soil quality reference values, global average soil concentrations and average upper continental crust concentrations. The contamination factor (CF), degree of contamination (Cdeg), potential ecological risk index (RI), geoaccumulation index (Igeo) and pollution load index (PLI) were calculated. The levels of Co, Cu and Ni in the tailings area exceeded the prevention values, soil quality reference values and average upper continental crust concentrations; however, the tailings area was considered unpolluted according to PLI and RI and presented a low potential ecological risk. The high concentrations of PTEs are associated with the geological properties of the area, and the presence of PTEs-rich minerals supports these results. For the urban and pasture areas, none of the 11 PTEs analyzed exceeded the prevention values established by the Brazilian National Environment Council.

Bioavailability of copper and nickel in naturally metal-enriched soils of Carajás Mining Province, Eastern Amazon, Brazil.

Naturally elevated contents of copper (Cu) and nickel (Ni) are found in soils worldwide, and their potential toxicity is better understood when geochemical reactive fractions are identified and monitored. Thus, this study aimed to assess the bioavailability of Cu and Ni and estimate environmental risks in naturally metal-enriched soils of Carajás Mining Province, Eastern Amazon, Brazil. For that, 58 surficial soil samples were analyzed for their extractable contents of Cu and Ni by Mehlich 1. Next, 13 soil samples were selected for additional single and sequential extractions, for the determination of metal content in the shoots of grasses naturally growing in these soils and for calculating the risk assessment code. Despite the naturally high total concentrations, the contents of easily available Cu and Ni are a minor fraction of total concentrations (up to 10.15%), and the reducible oxide and residual pools hold the major proportion of total content of metals. This contributed to low bioavailability, low environmental risk, and also to low concentrations of these metals on grasses collected in the field. Soil organic matter, Fe2O3, Al2O3 and clay content have a dominant role in metals retention on studied soils. Our findings on the bioavailability of Cu and Ni in a region of great economic relevance for Brazil are important not only for predicting the elements' behavior in the soil-plant system but also for refining risk assessments and to provide useful data for environmental quality monitoring.

Source and background threshold values of potentially toxic elements in soils by multivariate statistics and GIS-based mapping: a high density sampling survey in the Parauapebas basin, Brazilian Amazon.

A high-density regional-scale soil geochemical survey comprising 727 samples (one sample per each 5 × 5 km grid) was carried out in the Parauapebas sub-basin of the Brazilian Amazonia, under the Itacaiúnas Basin Geochemical Mapping and Background Project. Samples were taken from two depths at each site: surface soil, 0-20 cm and deep soil, 30-50 cm. The ground and sieved (< 75 µm) fraction was digested using aqua regia and analyzed for 51 elements by inductively coupled plasma mass spectrometry (ICPMS). All data were used here, but the principal focus was on the potential toxic elements (PTEs) and Fe and Mn to evaluate the spatial distribution patterns and to establish their geochemical background concentrations in soils. Geochemical maps as well as principal component analysis (PCA) show that the distribution patterns of the elements are very similar between surface and deep soils. The PCA, applied on clr-transformed data, identified four major associations: Fe-Ti-V-Sc-Cu-Cr-Ni (Gp-1); Zr-Hf-U-Nb-Th-Al-P-Mo-Ga (Gp-2); K-Na-Ca-Mg-Ba-Rb-Sr (Gp-3); and La-Ce-Co-Mn-Y-Zn-Cd (Gp-4). Moreover, the distribution patterns of elements varied significantly among the three major geological domains. The whole data indicate a strong imprint of local geological setting in the geochemical associations and point to a dominant geogenic origin for the analyzed elements. Copper and Fe in Gp-1 were enriched in the Carajás basin and are associated with metavolcanic rocks and banded-iron formations, respectively. However, the spatial distribution of Cu is also highly influenced by two hydrothermal mineralized copper belts. Ni-Cr in Gp-1 are highly correlated and spatially associated with mafic and ultramafic units. The Gp-2 is partially composed of high field strength elements (Zr, Hf, Nb, U, Th) that could be linked to occurrences of A-type Neoarchean granites. The Gp-3 elements are mobile elements which are commonly found in feldspars and other rock-forming minerals being liberated by chemical weathering. The background threshold values (BTV) were estimated separately for surface and deep soils using different methods. The '75th percentile', which commonly used for the estimation of the quality reference values (QRVs) following the Brazilian regulation, gave more restrictive or conservative (low) BTVs, while the 'MMAD' was more realistic to define high BTVs that can better represent the so-called mineralized/normal background. Compared with CONAMA Resolution (No. 420/2009), the conservative BTVs of most of the toxic elements were below the prevention limits (PV), except Cu, but when the high BTVs are considered, Cu, Co, Cr and Ni exceeded the PV limits. The degree of contamination (Cdeg), based on the conservative BTVs, indicates low contamination, except in the Carajás basin, which shows many anomalies and had high contamination mainly from Cu, Cr and Ni, but this is similar between surface and deep soils indicating that the observed high anomalies are strictly related to geogenic control. This is supported when the Cdeg is calculated using the high BTVs, which indicates low contamination. This suggests that the use of only conservative BTVs for the entire region might overestimate the significance of anthropogenic contamination; thus, we suggest the use of high BTVs for effective assessment of soil contamination in this region. The methodology and results of this study may help developing strategies for geochemical mapping in other Carajás soils or in other Amazonian soils with similar characteristics.

The role of protected and deforested areas in the hydrological processes of Itacaiúnas River Basin, eastern Amazonia.

To protect indigenous land and avoid the spread of deforestation in the Amazon, state and federal Brazilian agencies recognized several protected areas since the 1990s. However, the importance of these protected areas in the water cycle and the hydrologic connection with surrounding landscapes is little analyzed. In this study, we evaluated the role of preserved and deforested areas in the water balance in the Itacaiúnas River Basin using the MGB hydrological model. We estimated the impacts of land cover changes on evapotranspiration and discharge for four scenarios: Preserved (1984 land cover), Recent (2013 land cover, with 50% deforestation), Hypothetical deforestation of protected areas (70% deforestation) and complete deforestation of protected areas (79% deforestation). We showed that deforestation of the remaining preserved area could be responsible for a decrease of 23% (3.5 km³/year) in water transfer to the atmosphere by evapotranspiration. Furthermore, we showed that each 15% of deforestation occurring between the Preserved and Recent scenarios increased the average discharges by 5.4% (40 m³/s). Additionally, past land cover changes in the headwaters of the Itacaiúnas River Basin caused statistically significant changes in discharges inside the protected areas. This insight is considered important due to the association between increases in discharges and water quality issues. The results suggest that headwater areas of secondary drainages that run into the forested domains should be prioritized for reforestation programs. Likewise, the reforestation of nonprotected areas could be responsible for restoring ecosystem services, including hydrological functions, biodiversity and water quality.

Influence of seasonal variation on the hydro-biogeochemical characteristics of two upland lakes in the Southeastern Amazon, Brazil.

Limnological characteristics of the Violão and Amendoim lakes, in the Serra dos Carajás, Amazon, were studied interannually (2013-2014). Climate data indicate anomalous conditions during the 2013 rainy period with higher rainfall and lower temperature in the beginning (November). Lake levels were influenced after the first and second hour of each rainfall, which showed a strong synchronization between seasonal fluctuation of lake levels and local weather patterns. Based on the water quality, both lakes are classified as classes "1" and "2" in the CONAMA (Conselho Nacional do Meio Ambiente) scheme and as "excellent" to "good" in the WQI (Water Quality Index) categories. However, the limnology is distinctly different between the lakes and seasons. Higher trophic state and phytoplankton productivity were observed mainly during the rainy period in Violão Lake compared to Amendoim Lake. This may be due to deposition of leached nutrients in the former, mainly total phosphorus (TP), which was probably derived from mafic soils and guano. This is consistent with the significant positive correlation between Chlorophyll-a and TP at the end of the rainy period (March-April), whereas this was not observed in the beginning (November). This could possibly be a consequence of the more intense cloud cover, and unusual high rainfall that limits nutrient availability.

Four decades of land-cover, land-use and hydroclimatology changes in the Itacaiúnas River watershed, southeastern Amazon.

Long-term human-induced impacts have significantly changed the Amazonian landscape. The most dramatic land cover and land use (LCLU) changes began in the early 1970s with the establishment of the Trans-Amazon Highway and large government projects associated with the expansion of agricultural settlement and cattle ranching, which cleared significant tropical forest cover in the areas of new and accelerated human development. Taking the changes in the LCLU over the past four decades as a basis, this study aims to determine the consequences of land cover (forest and savanna) and land use (pasturelands, mining and urban) changes on the hydroclimatology of the Itacaiúnas River watershed area of the located in the southeastern Amazon region. We analyzed a multi-decadal Landsat dataset from 1973, 1984, 1994, 2004 and 2013 and a 40-yr time series of water discharge from the Itacaiúnas River, as well as air temperature and relative humidity data over this drainage area for the same period. We employed standard Landsat image processing techniques in conjunction with a geographic object-based image analysis and multi-resolution classification approach. With the goal of detecting possible long-term trends, non-parametric Mann-Kendall test was applied, based on a Sen slope estimator on a 40-yr annual PREC, TMED and RH time series, considering the spatial average of the entire watershed. In the 1970s, the region was entirely covered by forest (99%) and savanna (∼0.3%). Four decades later, only ∼48% of the tropical forest remains, while pasturelands occupy approximately 50% of the watershed area. Moreover, in protected areas, nearly 97% of the tropical forest remains conserved, while the forest cover of non-protected areas is quite fragmented and, consequently, unevenly distributed, covering an area of only 30%. Based on observational data analysis, there is evidence that the conversion of forest cover to extensive and homogeneous pasturelands was accompanied by systematic modifications to the hydroclimatology cycle of the Itacaiúnas watershed, thus highlighting drier environmental conditions due to a rise in the region's air temperature, a decrease in the relative humidity, and an increase in river discharge.