Prediction of heavy metals in polluted mangrove soils in Brazil with the highest reported levels of mercury using near-infrared spectroscopy.

Infrared reflectance spectroscopy has demonstrated potential as a tool for monitoring and preventing contamination in different environments. The objective of this study was to evaluate the usage of near-infrared spectroscopy for predicting heavy-metal contamination in mangrove soils from the Botafogo River estuary located in Pernambuco State, Northeastern Brazil. These soils exhibit the highest mercury (Hg) levels ever reported for Brazilian mangrove soils. Sixty-one samples (obtained at depths ranging from 0 to 5 cm) were collected and measured using near-infrared (1000-2500 nm) reflectance spectroscopy. Preprocessing methods were applied, and partial least squares regression was used to build prediction models for attributes such as clay content, soil organic matter (SOM), pH, Eh, and concentrations of Cr, Cu, Hg, Ni, Pb, and Zn. The models were evaluated using root mean squared error (RMSE), the adjusted coefficient of determination (R2adj), bias, the ratio of performance to interquartile distance (RPIQ), and Lin's concordance correlation coefficient (CCC). The best outcomes were noted for concentrations of Cr, Cu, Hg, Ni, and Pb (RPIQ > 2.5 and R2adj > 0.80); second-best outcomes were found for Zn and SOM (RPIQ > 1.5 and R2adj > 0.70). Clay content, pH and Eh exhibited the poorest outcomes (RPIQ < 1.5). The importance of spectral preprocessing is highlighted, notably with Savitzky-Golay derivatives and Multiplicative Scatter Corrections, which boosted performance for most of the variables. Near-infrared spectroscopy can be efficiently used to predict Cr, Cu, Hg, Ni, Pb and SOM and represents a technique complementary to traditional analyses.

Phosphorus in soils and fluvial sediments from a Cerrado biome watershed under agricultural expansion.

Over the past decades, lands alongside Gurguéia River have witnessed rapid expansion of soybean agriculture which has increased soil degradation and affected nutrient concentration in sediment, especially phosphorus (P). The present study aimed to quantify the P concentration in soils under different land uses (i.e., croplands, grasslands, and cerrado) and fluvial sediments (suspended sediment, channel bank, and riverbed sediments), assessing pollution over the main watercourse in cerrado biome Gurguéia watershed, located in Piauí State, Brazil. In total, 136 composite soil samples at a depth of 0-5 cm, under different land uses, as well as 51 composite fluvial sediment samples were collected over the watershed. The land use change from native cerrado had resulted in an increase of total phosphorus (TP) whose concentration was higher in cropland areas, followed by suspended sediment, channel bank, and riverbed sediments. This high concentration in cropland areas resulted from phosphate fertilizer inputs. The transfer of phosphorus to water bodies was evidenced, since an increase of TP was observed in suspended sediment, channel bank and riverbed  sediments. Mineralogical signatures in sediments were identified by X-ray diffraction analysis which showed the occurrence of kaolinite, illite, smectite, iron oxides, and other minerals in lesser proportions. The presence of 1:1 minerals was higher in riverbed sediments and downstream sampling points, while 2:1 minerals were present in higher proportions in suspended sediment and channel bank sediment, as well as at the upstream and middle sampling points. This finding shows that land use change from cerrado to cropland due to soybean agriculture expansion might increase P discharges from terrestrial to aquatic environments, with sediments being the major carrier of this element.

Influence of parent material on soil chemical characteristics in a semi-arid tropical region of Northeast Brazil.

Soil parental material is one of the main factors that influence pedogenesis. Several studies evaluated the relationship between the parent material and soil chemistry, but few studies have assessed such a relationship in semi-arid tropical regions. This investigation was carried out to assess the effect of different parent materials on the chemical composition and available concentrations of macronutrients and micronutrients, including potentially toxic elements (Cd, Cr, Ni, and Pb) in soils in a semi-arid tropical setting. The chemical composition of the soils inherited the geochemical signature of their parent materials. Quartz sandstones, augen gneisses, and peraluminous granites exhibited the lowest reservoirs of plant nutrients and formed sandy, acid, and infertile soils. On the other hand, alkaline soils and soils with high concentrations of nutrients formed on ultramafic rocks (harzburgite), marble, and anorthosite. The pH, clay content, and CEC were the main attributes of the soils governing the availability of macro and micronutrients. The low soil organic carbon contents did not influence the availability of the nutrients. The parent material also influenced the soil texture. Parent materials that are richer in silica formed more sandy soils. The availability of Cd, Cr, and Pb in soils was low; however, the elevated Ni concentrations of soils derived from ultramafic rocks may pose risks to the environment and human health. Cluster and discriminant analyses were used to discriminate the natural fertility of soils. These results are useful for the agro-pedological zoning of the Brazilian semi-arid tropical region and for land use planning.

Distribution of rare earth elements in soils of contrasting geological and pedological settings to support human health assessment and environmental policies.

Establishing quality reference values (QRVs) for rare earth elements (REEs) in soils is essential for the screening of these emergent contaminants. Currently, Brazil has the second-largest reserve of REEs, but data regarding background concentrations and distributions in soils remain scarce. The aim of this study was to establish the QRVs and assess the spatial distribution of REEs in soils, including REE fractionations and anomalies in (Piauí) state (251,529.186 km2), northeastern Brazil. This study reports the most detailed data on REE geochemistry in Brazilian soils. A total of 243 composite soil samples was collected at 0-20 cm depth. The mean background concentrations in soils followed the abundance of the earth's upper crust: Ce > La > Nd > Pr > Sm > Dy > Gd > Er > Yb > Eu > Tb > Lu. The ∑REEs (mg kg-1) showed the following order based on the individual mesoregions of Piauí state: Southeast (262.75) > North and Central-North (89.68) > Southwest (40.33). The highest QRVs were observed in the Southeast mesoregion. The establishment of QRVs based on the mesoregion scale improves data representativeness and the monitoring of natural REE values by identifying hot spots. Geostatistical modeling indicated significant local variability, especially in the Southeast mesoregion. The levels of these elements in this spatial zone are naturally higher than the other values across Piauí state and the mesoregion itself and indicate a high potential to exceed the QRVs. Our approach provides much needed data to help strengthen policies for both human health and environmental protection.

Potentially toxic elements and rare earth elements in sandy soils from the Brazilian Cerrado.

This study aims to determine the concentration of potentially toxic elements (PTEs) and rare earth elements (REEs) in Brazilian sandy soils under the Cerrado at the Parnaíba-São Francisco Basin transition. We also explored the geochemical correlation between these elements and pH, cation exchange capacity (CEC), total organic carbon (TOC), sand, clay, oxides from secondary minerals, and chemical index of alteration for each basin. Mineralogical, physical, and chemical analyses were used to examine PTE and REE geochemistry in six sand soil profiles from the Brazilian Cerrado. The background concentrations of these elements are low, but soils from the Parnaíba Basin have higher concentrations of PTEs than soils from the São Francisco Basin. In soils from the Parnaíba Basin, mainly Al2O3 has relevance in the V and Cr geochemistry, as these elements increase with increasing Al2O3 content. On the other hand, the REEs have CEC as a soil attribute of higher relevance in the geochemistry of those elements is soils from the Parnaíba Basin, and this relevance divides the TOC, Fe2O3, and TiO2 minerals from the clay fraction. In soils from the São Francisco Basin, the geochemistry of PTEs is possibly associated with kaolinite, especially Cu, V, and Zn. In contrast, the Ba concentration was associated with the presence of feldspar. Unlike soils from the Parnaíba Basin, the REEs do not correlate with the studied soil attributes, except for Ho and Lu. Ho had a positive association with Al2O3. Ho and Lu are negatively related to the presence of iron oxides.

Soil loss and sediment yield in a perennial catchment in southwest Piauí, Brazil.

Soil and water are vital natural resources. However, due to their indiscriminate use, these resources are being seriously threatened. Therefore, it is essential to manage them in a sustainable way and leave them for future generations. Population and agricultural areas have expanded, deforesting native landscapes for cultivation and pastures. As a result, soil loss from agricultural areas is increasing the amount of sediment transport in water courses. The objective of this study was to quantify soil loss and sediment yield from the Corrente dos Matões sub-basin (CMSB). These measurements are essential to quantify the environmental impact of advancing agricultural frontiers. The Universal Soil Loss Equation (USLE) was applied due to its wide use, compatibility with GIS, and data availability. The suspended sediment transport was calculated by collecting samples with DH-48 sampler. From the application of USLE, the average soil erosion contributed very little to sediment delivery in the watercourse, with a magnitude of only 0.37 t ha-1 year-1. The highest soil loss was associated with greater slope and was observed in areas with agriculture or under the absence of vegetation cover. The low transport of suspended sediments in CMSB is due to the existence of preserved sites. About 99% of the sub-basin had a low degree of erosion. The high degree of soil loss was attributed to the cliffs and the development of agricultural activities leaving the soil uncovered. This work will help identify the most susceptible areas to water erosion for optimizing the allocation of financial resources for the preservation of this natural resource.

Background concentrations and quality reference values for potentially toxic elements in soils of Piauí state, Brazil.

The background concentration of potentially toxic elements (PTE) in soils is influenced by the parent material composition and soil forming processes. The soil natural concentration of PTE is a first step to establish regulatory levels for the monitoring of these elements in soils suspected of contamination. In the present study, we performed a natural background concentration survey of PTE in soils of the Piauí state, Brazil. The study provides the basis for establishing soil quality reference values (QRVs) for a large area (over 251,000 km2) with different pedological features. A total of 262 geo-referenced soil samples (0.0-0.2 m) were collected in areas relatively undisturbed by human activity. The concentrations of Ba, Cd, Co, Cr, Cu, Fe, Mo, Ni, Pb, Sb, V, and Zn were determined by ICP-OES. Univariate statistical methods and multivariate exploratory techniques were used to understand the relationship between soil characteristics, geological features, and PTE concentrations in soils. The mean background concentrations of PTE in the soils were generally lower than those reported in other countries and/or other Brazilian states, and followed the order: Fe > Ba > V > Cr > Cu > Pb > Zn > Ni > Pb > Co > Mo > Sb > Cd. The main factors governing the concentrations of PTE in soils were the parent material and the soil texture. The different geological features in the study area influenced the spatial distribution of PTE and divided the state into three regions presenting low, high, and intermediate values. Given this geological and pedological complexity, we proposed establishing three sets of QRV rather than a single QRV for the whole state to avoid misinterpretation regarding the investigation of areas suspected of contamination. This background concentration survey contains a wealth of information that provides the basis for the soil guideline values in the state and supports future research on the impact of anthropogenic activities in soil contamination.

Near-infrared spectroscopy for the prediction of rare earth elements in soils from the largest uranium-phosphate deposit in Brazil using PLS, iPLS, and iSPA-PLS models.

The largest uranium-phosphate deposit in Brazil also contains considerable levels of rare earth elements (REEs), which allows for the co-mining of these three ores. The most common methods for REE determination are time-consuming and demand complex sample preparation and use of hazardous reagents. Thus, the development of a safer and faster method to predict REEs in soil could aid in the assessment of these elements. We investigated the efficiency of near-infrared (NIR) spectroscopy to predict REEs in the soil of the uranium-phosphate deposit of Itataia, Brazil. We collected 50 composite topsoil samples in a well-distributed sampling grid along the deposit. The NIR measures in the soils ranged from 750 to 2500 nm. Three partial least squares regressions (PLSR) were selected to calibrate the spectra: full-spectrum partial least squares (PLS), interval partial least squares (iPLS), and successive projections algorithms for interval selection in partial least squares (iSPA-PLS). The concentrations of REEs were measured by inductively coupled plasma optical emission spectroscopy (ICP-OES). In addition to raw spectral data, we also used spectral pretreatments to investigate the effects on prediction results: multiplicative scatter correction (MSC), Savitzky-Golay derivatives (SG), and standard normal variate transformation (SNV). Positive results were obtained in PLS for La and ΣLREE using MSC pretreatment and in iSPA-PLS for Nd and Ce using raw data. The accuracy of the measurements was related to the REE concentration in soil; i.e., elements with higher concentrations tended to present more accurate results. The results obtained here aim to contribute to the development of NIR spectroscopy techniques as a tool for mapping the concentrations of REEs in topsoil.

Combining geospatial analyses to optimize quality reference values of rare earth elements in soils.

High pedological and geological variability can trigger the formation of REE hotspots, causing a need to optimize the establishment of quality reference values (QRVs). Thus, we determined the background concentrations of REEs in the soils of an emerging Brazilian state and used a combination of Moran's I and indicator kriging to identify REE hotspots and determine QRVs. A total of 100 composite soil samples was collected at a 0.20 m depth to establish background concentrations, QRVs, and spatial distribution and to elaborate probability maps for REEs. The QRVs established for soils were the following (mg kg-1): La (27.21), Ce (57.26), Pr (10.49), Nd (24.29), Sm (4.75), Eu (0.90), Gd (4.22), Tb (0.82), Dy (1.54), Ho (0.38), Er (1.23), Yb (1.07), Lu (0.24), Y (10.65), and Sc (3.70). It was possible to draw attention to the Northwest and Southwest regions of the Rio Grande do Norte (RN) state, due to the formation of REE hotspots, indicated by Moran's I, and a high tendency to exceed the QRVs, confirmed by the indicator kriging. The high background concentrations and geochemical patterns for REEs showed that a single QRV for each REE and the entire state can neglect specific environmental characteristics and misrepresent the natural geochemistry of the soil. Thus, specific QRVs were established to optimize the monitoring of natural REE values by identifying hotspot areas. The criteria established here may be useful for other groups of potentially toxic elements, provided that observations meet the requirements of the spatial autocorrelation and kriging analyses. Graphical abstract.

Thorium content in soil, water and sediment samples and fluvial sediment-associated transport in a catchment system with a semiarid-coastal interface, Brazil.

Thorium (Th) is one of the main sources of natural radiation to ecosystems. However, data regarding Th concentrations in rocks, soil, water and sediments are currently scarce. Accordingly, this study aimed to establish background concentrations and quality reference values (QRVs) for Th in the environmentally impacted Ipojuca River catchment in Brazil, where the weathering of granites releases Th into the environment. Additionally, the study aimed to calculate Th fluxes in water, and both bed and suspended sediment. The mean Th concentration in the study catchment soils was 28.6 mg kg-1. The QRV for Th was estimated to be 21 mg kg-1 and 86.3 Bq kg-1. Bed and suspended sediment-associated concentrations ranged from 2.8 to 32.9 mg kg-1. Suspended sediment-associated discharge (3.42 t year-1) accounted for more than 99% of the total Th flux, while the dissolved phase transport was negligible in comparison. At the downstream cross section in the study catchment, suspended sediment samples exhibited Th concentrations similar to those observed in rivers impacted by mining activities. The discharge of sediment to the ocean from the study area is mainly triggered by soil erosion processes in the hotspot region (middle-inferior course). It is essential to identify Th hotspots before establishing environmental policies regarding human health and environmental protection.

Watershed scale assessment of rare earth elements in soils derived from sedimentary rocks.

Despite the rare earth elements (REEs) being considered as emerging contaminants, their natural values and possible anthropogenic enrichments in soils have not been studied well in Brazil. The intensive use of conditioners and fertilizers in agricultural frontiers from Brazilian Cerrado can increase the concentration of REE in soils of the region. In this context, the objectives of this study were to determine the natural content and establish quality reference values (QRV) for REEs in soils of a watershed from Brazilian Cerrado composed of sedimentary rocks and to evaluate the influence of agricultural cultivation and the spatial variability of these elements. Thirty and twenty-six composite soil samples were collected under native vegetation and soybean cultivation, respectively. The background concentrations followed the order (mg kg-1) Ce > Nd > La > Pr > Sm > Yb > Er > Eu > Dy. The QRVs established were as follows (mg kg-1): La (1.76), Ce (5.20), Pr (0.74), Nd (1.35), Sm (0.38), Eu (0.06), Dy (0.15), Er (0.12), and Yb (0.14). Lantanium, Ce, and Er exhibited strong spatial dependence, while Eu, Dy, and Yb showed weak or total absence of spatial dependence. The spherical model was most suitable for the spatial characteristics of REEs. The parent material, mainly characterized by soils derived from sedimentary rocks (i.e., sandstone), was the primordial source of REEs for soils and that there was no or little effect of agricultural practices on these levels. Our data reinforced the need for geochemical mapping at the watershed scale, since they are important conservation units.

Bed and suspended sediment-associated rare earth element concentrations and fluxes in a polluted Brazilian river system.

Rare earth elements (REEs) have been recently recognized as emergent pollutants in rivers. However, data regarding REE fluxes in association with either bed or suspended are scarce. To address this knowledge gap, we determined the concentrations and fluxes of La, Ce, Pr, Nd, Sm, Eu, Gd, Yb, Lu, Dy, Er, Ho, Tb, and Tm in bed and suspended sediment samples of a representative polluted Brazilian River. Sediment-associated data on REEs were placed in the context of corresponding background concentrations in soils under natural conditions along the Ipojuca watershed. Light rare earth elements (LREEs) comprised more than 94% of the total REEs associated with bed and suspended sediments. Suspended sediments accounted for more than 95% of the total REE flux. The Ce and Nd fluxes of about 7 t year-1 underscore the importance of including REEs in future estimations of global suspended sediment-associated element fluxes. In contrast, bedload often transported less than 0.0007 t year-1 of each REE. The main sources of pollution in the Ipojuca River are anthropogenic, likely due to domestic effluent and waste water from industrial and agricultural operations-major causes of sediment-associated Gd transport in polluted streams.

Watershed-scale assessment of background concentrations and guidance values for heavy metals in soils from a semiarid and coastal zone of Brazil.

Determining heavy metal background concentrations in soils is fundamental in order to support the monitoring of potentially contaminated areas. This is particularly important to areas submitted to high environmental impact where an intensive and local monitoring is required. To this end, the aim of this study was to establish background concentrations and quality reference values (QRVs) for the heavy metals Cd, Cr, Cu, Fe, Mn, Ni, Pb, Zn, As, and Hg in an environmentally impacted watershed from Brazil. Geochemical associations among Fe, Mn, and trace elements were also assessed to provide an alternative tool for establishing background concentrations. A total of one hundred and four samples comprised twenty-six composite soil samples from areas of native forest or minimal anthropic influence. Samples were digested (USEPA method 3051A), and the metals were determined by ICP-OES, except for As and Hg measured by atomic absorption spectrophotometer. Background concentrations of heavy metals in soils had the following decreasing order: Fe > Mn > Zn > Cr > Pb > Ni > Cu > As > Cd > Hg. These values were usually lower than those observed in the international and national literature. The QRVs for Ipojuca watershed followed the order (mg kg(-1)) Fe (13,020.40) > Mn (91.80) > Zn (30.12) > Cr (15.00) > Pb (13.12) > Cu (3.53) > Ni (3.30) > As (0.51) > Cd (0.08) > Hg (0.04). Significant correlation among Fe, Mn, and heavy metals shows that solubilization by the method 3051A provides a reasonable estimate for predicting background concentrations for Cd, Cr, and Cu as well as Zn, Cr, Cu, and Ni.

Trace element fluxes in sediments of an environmentally impacted river from a coastal zone of Brazil.

Data regarding trace element concentrations and fluxes in suspended sediments and bedload are scarce. To fill this gap and meet the international need to include polluted rivers in future world estimation of trace element fluxes, this study aimed to determine the trace element fluxes in suspended sediment and bedload of an environmentally impacted river in Brazil. Water, suspended sediment, and bedload from both the upstream and the downstream cross sections were collected. To collect both the suspended sediment and water samples, we used the US DH-48. Bedload measurements were carried out using the US BLH 84 sampler. Concentrations of Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn were determined by inductively coupled plasma (ICP-OES). As and Hg were determined by an atomic absorption spectrophotometer (AA-FIAS). The suspended sediments contributed more than 99 % of the trace element flux. By far Pb and to a less extent Zn at the downstream site represents major concerns. The yields of Pb and Zn in suspended sediments were 4.20 and 2.93 kg km(2) year(-1), respectively. These yields were higher than the values reported for Pb and Zn for Tuul River (highly impacted by mining activities), 1.60 and 1.30 kg km(2) year(-1), respectively, as well as the Pb yield (suspended + dissolved) to the sea of some Mediterranean rivers equal to 3.4 kg km(2) year(-1). Therefore, the highest flux and yield of Pb and Zn in Ipojuca River highlighted the importance to include medium and small rivers-often overlooked in global and regional studies-in the future estimation of world trace element fluxes in order to protect estuaries and coastal zones.