δ13C, δ15N and TOC/TN as indicators of the origin of organic matter in sediment samples from the estuary of a tropical river.

The present study aimed to determine the total organic carbon (TOC), total nitrogen (TN), the carbon­nitrogen ratio (TOC/TN), carbon isotope (δ13C), and nitrogen isotope (δ15N) in five sediment cores collected from upstream to downstream of the Rio Serinhaem estuary, State of Bahia, Northeast Brazil, in order to investigate the origin of the deposited organic matter (OM).Significant positive correlation was found between TOC and NT (rs = 0.75); TOC/TN and TOC (rs = 0.64); δ15N and TOC (rs = 0.72); and δ15N and TOC/TN (rs = 0.63). The values of δ13C and δ15N found are characteristic of terrestrial sources. The TOC/TN ratio confirmed the data found for δ13C and δ15N, which recorded the origin of organic matter from terrestrial C3 type plants. Upstream of the estuary, the highest means of TOC/TN were found (T1 = 36.9 and T2 = 24.4), as reflected by the increase in TOC content or reduction in TN. The OM along the estuary is predominantly from plants with a C3 photosynthetic pattern, indicating that the Serinhaem River estuary is considered a relatively well-preserved environment.

Evaluation of metal contamination in mangrove ecosystems near oil refining areas using chemometric tools and geochemical indexes.

The northern and northeastern portion of the Todos os Santos Bay (TSB) is known for the presence of an oil refinery in addition to the development of other activities with significant potential for impact on the environment. 30 samples of superficial mangrove sediment were collected in two different locations: on the banks of the São Paulo River near the Landulpho Alves Mataripe Refinery (RLAM) and at Caboto Beach, a place that was once a control point in studies of metal pollution. After the determination of potentially toxic elements (Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, Ti, V, Zn), the quality of the sediment was evaluated using the concentrations of these elements associated with geochemical parameters (TOC, P, S, and granulometry). In this way, the pollution indexes (EF, Igeo, PN) were calculated in addition to the comparison with the guide values for the sediment quality (TEL, PEL, ERL, ERM). Among the elements analyzed, Cu also showed levels (92.71-97.54 mg kg-1) very close to PEL (108 mg kg-1). At 13 sampling points, Cr concentrations were higher (56.16-66.01 mg kg-1) than TEL (52.3 mg kg-1). Ba showed significant concentrations in 6 samples collected on the São Paulo River, a region close to the oil refining area. The enrichment factor (EF) showed that most elements did not show enrichment, except for Zn. Through Igeo there was a tendency towards serious pollution of Ba, Cu, and Zn; moderately polluted by Cr. Principal component analysis (PCA) and Spearman's classification showed a correlation greater than 70% between the variables. According to Nemerow Synthetic Pollution (PN), both areas are polluted by Al, Ba, Cr, Cu, Fe, Mn, Ni, Ti, V, and Zn.

Evaluation of the concentrations of elements at trace level in the Serinhaem River estuary, Bahia, Brazil, using chemometric tools.

The Serinhaém River estuary is located in the Environmental Protection Area (EPA) of Pratigi, in the State of Bahia, Brazil, which is recognized for being a relatively well-preserved environment. In this work, the levels of aluminum (Al), arsenic (As), barium (Ba), cobalt (Co), chromium (Cr), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), lead (Pb), vanadium (V), and zinc (Zn) were determined to evaluate the behavior of these chemical elements through geochemical parameters. Eighty-one sediment samples were collected in five sediment cores along the estuarine region. The results of the composition of the Serinhaém river basin showed high levels of Fe, Al, and Mn in the sediment samples. By using Principal Component Analysis, it was observed that 55.8% of the elements have a significant correlation with Fe, Al, and Mn, which may have the same origin or be associated with Fe and Mn oxy-hydroxides, and aluminosilicates. Although Cr, As, and V are correlated with Fe, Mn, and Al, their concentrations are above those established by NOAA, suggesting adverse effects on biota. Barium concentrations increased toward the outfall, where it meets the Camamu Bay, which is naturally enriched with this element. It was also possible to observe that along with the vertical profile, there were no variations in the concentrations of the elements, while along the estuary, it was possible to verify that the cores differ from each other. The estuary of the Serinhaém River can be considered to be influenced relatively little by human activities, and its concentrations can be considered as a base level for this coastal region.

Assessment of toxicity of metals in river sediments for human supply: Distribution, evaluation of pollution and sources identification.

Ten surface sediments collected from Joanes River, Bahia, Brazil in rainy and drought periods in 2019 were evaluated according to the enrichment factor (EF), potential ecological risk index (RI), potential contamination index (PCI), pollution load index (PLI), and index of geoaccumulation (Igeo). Initially the dry sediment was subjected to granulometric analysis and determination of the concentration of organic matter. Then, the samples were digested in HNO3 and analyzed by Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) to determine the metals cadmium (Cd), copper (Cu), chromium (Cr), nickel (Ni), lead (Pb) and zinc (Zn). Zn and Cu were classified in that order as the most contaminated elements in most sediment. Comparison of the total metal concentrations with the threshold (TELs) and probable (PELs) effect levels in sediment quality guidelines suggested a more worrisome situation for Zn (648.83-1415.90 µg g-1; PELZn = 315 µg g-1), of which concentrations were occasionally associated with adverse biological effects in four sediments, followed by Cu in five sediments during dry and rainy periods; while adverse effects were rarely associated with Cd, Cr, Ni, and Pb. In another evaluation, Cd, Cu, Cr, and Zn could be considered the most dangerous in the entire river, as they were classified in the high levels of contamination by the PCI, associated with serious adverse effects in most samples. In an assessment regarding the ecological risks in the study environment, the sediment samples remained below the limit established by the risk index (IR). The Zn presented moderately severe enrichment (6.78-11.83) in all the collection stations in the dry and rainy periods, followed by the Cd that presented moderate enrichment (2.23-4.17), whose values exceeded almost 1000 times the background at one site. Through the PCA it was possible to evidence the existing correlation between metals, organic matter, and silt and clay fraction. The results obtained in the PCA represented more than 80% of the variance between the data. The environmental risk assessment revealed a significant increase in the risk associated with metals during the rainy season. This is probably due to the greater supply of organic matter from the leaching of the margins.

Geochemical evaluation of potentially toxic elements determined in surface sediment collected in an area under the influence of gold mining.

In this present paper, the distribution of toxic metals and sediment quality were evaluated in five sampling points of the Itapicuru-Mirim River located in the city of Jacobina, Bahia, Brazil. The concentration of the elements arsenic (As), cadmium (Cd), chromium (Cr), copper (Cu), iron (Fe), mercury (Hg), manganese (Mn), nickel (Ni), lead (Pb), and zinc (Zn) were determined from sediment samples collected from the superficial layer (0-10 cm) in November 2013. After the samples' total decomposition, the total concentration of metals was determined by inductively coupled plasma optical emission spectrometry (ICP OES), except for Hg, which was measured by inductively coupled plasma atomic emission spectrometry (ICP AES). A geochemical evaluation of sediment quality was performed using enrichment factor (EF), geoaccumulation index (Igeo), and pollution load index (PLIThe results of the total concentrations in the analyzed sediment samples were compared with the threshold effect levels (TELs) and probable (PELs) effect levels (PELs) in sediment quality guidelines (SQGs). For the fraction <75 µm, the decreasing order for the metal concentrations was (ppm): Fe (10.86%) > Mn (120.8) > Cr (122) > Zn (76.5) > Pb (49.6) > Cu (32.6) > Ni (28.6) > Hg (0.31) > Cd (0.13). Igeo suggested a moderate to seriously polluted category for Hg and moderately polluted for Cu. Generally, the results indicated probable risks to the biota caused by Cr, Ni, Pb, and Hg metals. However, only Hg, Cd, and Cu were of anthropogenic origin. Although the sediments are relatively preserved from pollution by these metals, there is a progressive deterioration of this compartment downstream of the Itapicuru-Mirim River in the city of Jacobina.

Combining geochemical and chemometric tools to assess the environmental impact of potentially toxic elements in surface sediment samples from an urban river.

This article investigates sediments collected from the banks of the Subaé River located in Todos os Santos Bay in the state of Bahia, Brazil, in 2018, twenty-five years after the closing of a former lead alloy processing plant. Ten sediment samples were collected at different points of the course of the river and its estuarine region. Chemometric tools were used to determine geochemical correlations between the organic matter content and concentration of sulfides and potentially toxic metals. The inorganic geochemical variables (enrichment factor [EF]) used in this evaluation were concentrations of the Pb, Cd, Cu, Zn, and Ni. Chemical element analyses were performed using ICP-OES. To assess the interaction between metals and sulfide or metals and organic matter, concentrations of Pb, Cd, Cu, Zn, Ni, sulfide, and the silt-clay fraction constituted the organic geochemical parameters selected to characterize the amount of organic matter present in Subaé River sediment samples, determining the carbon content (%TOC) to compose the matrix of the principal component analysis (PCA) and hierarchical cluster analysis. PCA showed that 88.3% of the samples were representative for assessing correlations between geochemical variables. A tendency toward binding was found among Cu, Cd, Ni, and sulfide, as well as the silt-clay fraction. The concentrations (mg kg-1) of lead, zinc, and copper were higher in both collection campaigns, ranging from 4.72 to 31.34, 12.76 to 54.24, and 5.34 to 31.37, respectively. Pb and Zn were presented in elemental form when assessed as a function of the pH and Eh of the environment. Except for Cd (EF: 0.51 to 5.49), the other elements exhibited little or no potential pollution in the aquatic environment of the Subaé River.

Evaluation of the bioavailability of potentially toxic metals in surface sediments collected from a tropical river near an urban area.

The objective of this study was to evaluate the bioavailability of the metals cadmium, copper, lead, nickel, and zinc from sediment samples collected in the Paraguaçu river between the cities of Cachoeira and São Félix in the state of Bahia in Brazil. The method used was the acid extraction of volatile sulfides and metals extracted simultaneously (AVS-SEM) as described in the literature. For the extraction of sulfide, an argon drag system was used after acidification of the samples with HCl, releasing the volatile sulfides collected in the basic solution. Its determination was made by molecular absorption spectrophotometry using the methylene blue method. For quantification of the metals, the sediment with acid was filtered and the residual solution was analyzed by inductively coupled plasma mass spectrometry (ICP MS) in which the elements that were associated with the sulfide were released in solution. The bioavailability evaluation was done by the relation between the sum of the concentrations of the metals in solution (SEM) and the concentration of sulfide in each sample (AVS). When the ∑SEM/AVS ratio is >1, the medium is considered contaminated by the high bioavailability of the metals to other environmental compartments. In the samples collected in the Paraguaçu river in two campaigns, with an ∑SEM/AVS ratio of 0.007 to 1.082, the last value being the only critical>1, while the other quantities in the metallic phase were not available for a biota. By comparing the metal concentration data with the internationally established tolerance limits, all the values found were below the critical values, presenting no toxic risks to the surrounding ecosystem.