Search

This study evaluates contamination and potential ecological risk in Ilha Grande Bay (BIG) in southeastern Brazil. To achieve these objectives, we analyzed physicochemical, sediment textural, and geochemical data from 134 stations distributed throughout the bay. The results reveal significant environmental degradation in the coastal areas of Paraty, Saco do Mamanguá, Angra dos Reis City, and Abraão Cove (at Ilha Grande island). These regions exhibit moderate to significant pollution from metals. High potential ecological risk was identified in approximately 87 stations (about 65 %), primarily due to Hg, Cd, and As, with additional contributions from Tl, Ni, and Cu. Evidence indicates that concentrations of these chemical elements have been increasing in recent years. Among these metals, Hg is particularly concerning because of its toxicity and persistence in the environment. The primary sources of contamination in BIG appear to be urban and industrial effluents, metalworks, the combustion of coal and oil, and the incineration of waste and sewage sludge, all of which have contributed to rising pollution levels over the past two decades. Sedimentary processes also facilitate the formation of pollution patches. It is crucial to address the recent escalation in contamination by effectively controlling pollution sources. This study recommends revising the methods and standards for metals established by national and international legislation to better assess sediment quality in marine environments., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier Ltd. All rights reserved.)

The 87 Sr/ 86 Sr isotope ratio has been widely used as an indicator of provenance and migration of aquatic animals, and has applications in other areas such as in environmental and forensic studies. However, the modeling of the spatial distribution in the Amazon basin is still incipient, preventing large-scale applications. In this study, we present a baseline of the 87 Sr/ 86 Sr isotope ratio in surface waters of the Amazon basin to infer the provenance and migration patterns of fish. We have compiled an extensive 87 Sr/ 86 Sr database of water samples from the Amazon basin, with data obtained from scientific publications and from field surveys. Next, we developed a geostatistical model, based on spatial interpolation (IDW), to estimate the 87 Sr/ 86 Sr ratio in unsampled locations, considering the influence of geology. Surface river waters in the Amazon show a high isotopic heterogeneity, associated with the region's geology (p < 0.005). Lower isotope ratios are related to waters draining more recent structures, such as the sub-basins of the Andean region, while higher isotope ratios are related to waters draining older crystalline terrains, such as the Guiana and Brazilian Shields. We show a linear relationship between the predicted and observed values (r 2  = 0.81), demonstrating the high accuracy of the modeled data and its potential use in various other studies. The acquisition of additional 87 Sr/ 86 Sr data, along with the integration of new geospatial products, can improve estimates and accuracy in interpretations of strontium geospatial behavior in micro- and macroregions., Competing Interests: Declaration of competing interest The authors declare the following financial interests/personal relationships which may be considered as potential competing interests: Has patent pending to. If there are other authors, they declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier B.V. All rights reserved.)

A reliable response of bioindicators to environmental variation is a cornerstone for effective bioassessment and biomonitoring. Fish and aquatic macroinvertebrates are widely used as bioindicators of different human impacts in freshwater ecosystems, but the cost-effectiveness of their usage can be improved through the use of surrogates. We investigated congruence patterns between using different taxonomic and numeric resolutions for aquatic macroinvertebrates and fish to assess community-environment relationships. We also tested whether dataset characteristics (e.g., area sampled, species pool) could explain the variation in the effectiveness of using different taxonomic and numerical resolutions. We used a Brazilian nationwide database encompassing multiple datasets with a gradient of riparian deforestation each. Our findings suggest that families and genera can effectively represent macroinvertebrate genera and fish species, respectively, when using community matrices for assessing community-environment relationships, with an acceptable loss of information. EPT (Ephemeroptera, Plecoptera, and Trichoptera) and Characiformes or Siluriformes may be used as a surrogate, in some cases, for the entire assemblages of macroinvertebrates and fish, respectively, but their use may result in higher loss of information. Presence-absence data also presented a minimal loss of information compared to abundance data, for both macroinvertebrates and fish. The variation in congruence levels among macroinvertebrate datasets was less predicted by dataset characteristics than fish. Across distinct resolutions, on average, 10 % and 19 % of the variation in community composition of macroinvertebrates and fish, respectively, was explained by broad-scale environmental variables, and the effect size was negatively affected by the dataset's sample size and spatial extent for fish. Whereas identification at species (fish) and genus (macroinvertebrates) level and quantification of all individuals still provide the best scenario, we provide evidence that coarser taxonomical resolution and presence-absence data can be used as cost-effective alternatives to facilitate biomonitoring and bioassessment of freshwaters in the Neotropical region impacted by deforestation., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier B.V. All rights reserved.)

Understanding the patterns and mechanisms of biodiversity and its organization in space is essential for developing effective conservation strategies. Zeta diversity is an index of how taxa are shared by several sites, providing information on how ecological filters, including anthropogenic disturbances, influence biodiversity distribution. This study documents how anthropogenic disturbances at multiple spatial extents affect the spatial variation of benthic macroinvertebrate assemblages in lotic ecosystems. To test the relation between zeta diversity and anthropogenic disturbances, we used three disturbance metrics. (a) For in-stream disturbances, we used the percentage of fine sediment in the substrate (PCT&#95;FN). (b) For local/riparian disturbances, we used the Local Disturbance Index (LDI). (c) For catchment disturbances we used the Catchment Disturbance Index (CDI). Our results showed that differing anthropogenic disturbances were differently important for spatial biodiversity variation in benthic macroinvertebrate assemblages. Relatively rarer taxa were usually more susceptible to in-stream and local/riparian-scale disturbances or local environmental filters. On the other hand, relatively common taxa were usually more related to catchment-scale disturbances or landscape resistance to dispersal. These results indicate that conservation efforts to maintain headwater ecosystem biodiversity must incorporate multiple spatial extents because relatively rare and relatively common taxa appear to be affected to different degrees by different anthropogenic disturbances at different spatial extents., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2025 Elsevier B.V. All rights reserved.)

The knowledge of metals concentration in upwelling areas are a concern due the higher productivity of these areas In Cabo Frio Upwelling-Downwelling System (CFUS) is high primary productivity area and has been identified as an Hg hotspot to biota in SE Brazil that has been susceptible to Hg inputs, due to growing industrialization in the region. To investigate the concentration of Hg and Se metals, as well as the trophic transfer of these metals, the present study investigated Hg and Se concentrations in 64 samples collected in net mesh of >20, >64, >150 and >300 μm, in 2012, in the region's water masses. Higher mean Hg concentrations were found in zooplankton, 0.15 ± 0.09 μg g -1 (>300 μm) and 0.18 ± 0.1 μg g -1 (>150 μm), compared to phytoplankton, 0.11 ± 0.11 μg g -1 (>64 μm) and 0.06 ± 0.07 μg g -1 (>20 μm), and the calculation of the biomagnification factor (BMF) indicated that there was a process of magnification and trophic transfer. An opposite trend was found for Se in phytoplankton: higher average Se concentrations were observed in phytoplankton, 93.0 ± 65.2 μg g -1 (>64 μm), 93.8 ± 96.4 μg g -1 (>20 μm), compared to zooplankton, 91.1 ± 67.3 μg g -1 (>300 μm), 97.3 ± 71.3 μg g -1 (>150 μm). A positive linear relationship for the Hg:Al vs P:Al ratios was identified and indicated intracellular incorporation of Hg according to plankton size. Anthropogenic Hg sources were identified in the plankton samples by comparison with the sediment background values for the CFUS. Upwelling waters probably increased the availability of Hg and Se, these elements tend to bioaccumulate 10 to 100 times more than in areas with the influence of upwelling, due to fertilization and the increase in primary production., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier B.V. All rights reserved.)

Marajó Island, an environmental protection area for sustainable use in the Brazilian Amazon, was the first region in Brazil to apply the pesticide DDT, a persistent organic pollutant (POP), to control malaria outbreaks. This study investigated background levels of various POPs, including o,p'- and p,p'-DDT and their primary metabolites (o,p'- and p,p'-DDE, o,p'- and p,p'-DDD), as well as hexachlorocyclohexane (α-, β-, γ-, δ-HCH), using estuarine surface sediments and sediment cores from areas influenced by urbanization and agriculture. All samples were collected during the dry season (September 2014). Surface sediments exhibited ΣDDT concentrations up to 2.71 ng g⁻ 1 , with isomeric ratios indicating past DDT application and contributions from dicofol. Sediment profiles revealed alternating aerobic and anaerobic degradation processes of DDT. Other organochlorinated contaminants were not detected. The presence of γ-HCH as the main isomer (0.24 to 0.90 ng g⁻ 1 ) in surface samples suggests recent lindane application as a wood preservative or cattle parasite treatment. A dated sediment core revealed historical contamination of early DDT tests in the Amazon during the mid-1940s. Increasing ΣDDT concentrations (up to 12.3 ng g⁻ 1 ) were identified in the 1970s, coinciding with the intensification of DDT use for public health campaigns, which lasted until 2009 and reached the highest ΣDDT flux. Legal restrictions on the use and commercialization of POPs, along with natural degrading processes, likely led to decreased accumulation and limited ecological risks. Furthermore, the low concentrations of POPs suggested biodegradation and dispersion from northeast to southeast., Competing Interests: Declarations. Ethical approval: This study was authorized by the Chico Mendes Institute for Biodiversity (ICMBio/SISBIO 49140–1). Consent to participate: The authors consent to participate in this study. Consent for publication: The authors consent to publish the study. Competing interest: The authors declare no competing interests., (© 2024. The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature.)

The Paranaguá Estuarine System (PES) is an extensive subtropical estuarine system on the Southern Brazilian coast. It encompasses one of the last preserved areas of the Atlantic Forest and is recognized by UNESCO as a Natural Heritage site. This study evaluates the human impact of rapid and unplanned urbanization, an inefficient sewage system, and two port complexes by using linear alkylbenzenes (LABs) as a molecular marker for sewage input. The LAB analyses included Soxhlet extraction, clean-up, and quantification, which was performed using a gas chromatograph coupled to a mass spectrometer. The concentrations of total LABs (∑LABs) in the dry-weight sediments of PES ranged from below detection limits to 42.7 ng g -1 , with an average of 6.5 ± 7.8 ng g -1 . The primary sources of LABs are rivers surrounding the city of Paranaguá, which receive sewage inputs. In contrast, the input of allochthonous organic carbon and fine sediments is primarily associated with discharges from the Antonina River watershed. The recent unplanned occupation of estuarine margins, with untreated or inadequately treated sewage discharged directly into the environment or cesspools, explains the low degradation levels of LABs found in some sectors of the PES. The current concentrations of LABs, lower than those along the Brazilian coast and in densely populated coastal countries, suggest good sediment quality. This study shows that LABs can serve as a geochemical tool for tracing sources and distinguishing impacts related to population density in one of the largest preserved subtropical estuarine areas in the Southern Hemisphere., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

The Sepetiba Bay (SB, SE Brazil) is a highly anthropized and industrialized area that has experienced severe environmental degradation in recent decades. This study applies a multiproxy approach to document the response of living benthic foraminifera to environmental stress and to infer the Ecological Quality Status (EcoQS) in SB. Our methodology involved a comprehensive comparison of the density and percentage of benthic foraminiferal species with physicochemical, textural, and geochemical data, specifically the concentrations of potentially toxic elements (PTEs). We also statistically compared two geochemical indices, the pollution load index (PLI) and the potential ecological risk index (PERI), with two ecological indices, the Tolerant Species Index (TSI) and the Exp(H'bc). The TSI and the Exp(H'bc) indices are significantly correlated with the environmental stressors in Sepetiba Bay, namely the PTEs concentrations (As, Cd, Pb, and Zn). The most tolerant species to the enrichment of PTEs and organic matter are Ammonia tepida (Cushman, 1926), Elphidium excavatum (Terquem, 1875), Ammonia buzasi Hayward and Holzmann, 2021 and Ammonia rolshauseni (Cushman and Bermúdez, 1946). The Exp(H'bc) and TSI reveal that most stations located in the inner zone and near the margins of the bay have poor and bad EcoQS, which agrees with the distribution of the environmental stressors. Thus, the current environmental conditions of the inner area of Sepetiba Bay are of great concern. This work also shows that using the TSI and the Exp(H'bc) indices, it is possible to classify EcoQS in transitional coastal environments in the North and South Atlantic transitional waters. This work has relevant scientific and social implications due to its importance in biomonitoring and the management of the coastal regions., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

This study identified the occurrence of Holocene chronology hiatuses in the sedimentary record of the Patos-Mirim system caused by river avulsion processes, as well as evidence of sharp anthropogenic changes in the surrounding region of the lagoon water bodies. The presence of chronology hiatuses demonstrates the importance of considering the disturbance effect of paleo-drainage processes on the paleoenvironmental resolution and expression of the sedimentary record of such coastal plains. Anthropogenic activities especially those related to agriculture and forestry have increased significantly during the great acceleration, resulting in modifications of both the landscape and the environmental conditions of the lagoon bodies. Such impacts were clearly reflected in the sedimentary record where abrupt changes in palynological trends, sedimentary DNA, isotopic and granulometric analyses were inferred. The climatic conditions combined with regressive sea level can explain the chronology hiatuses. Pollen analyses demonstrated changes in the landscape, particularly indicated by the shift from Cyperaceae to Poaceae dominance after the 1960 CE. Therefore, all proxies together demonstrate the modification in the landscape and changes in the environment, clearly influenced by anthropogenic action from unsustainable agricultural practices., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024. Published by Elsevier B.V.)

The improvement of water management requires monitoring techniques that accurately evaluate water quality status and detect the effects of land use changes on water chemistry. This study aimed to evaluate how multivariate statistical methods and water quality indices can be applied together to evaluate the processes controlling water chemical composition and the overall water quality status of a tropical watershed. Thirty-four water samples were collected in the Formoso River basin, located on the border of the Amazon Forest. Water parameters were measured in situ using a multiparameter and in the lab using spectroscopic and volumetric techniques. The water quality dataset was interpreted through principal component analysis, multivariate linear regression, and water quality indices. Statistical methods allowed us to identify the sources and geochemical processes controlling water quality chemistry, which were carbonate dissolution, runoff/erosion, nutrient input due to anthropogenic activities, and redox reactions in flooded zones. They were also used to create linear functions to evaluate the effects of land use changes on the geochemical processes controlling water chemistry. Conversely, the water quality indices provide information about the overall condition of the water. The Weight-Arithmetic Quality Index correctly evaluates water suitability for its multiple uses, according to the Brazilian guidelines. Conversely, the Ontario Water Quality Index is not suitable to evaluate the water quality of tropical rivers, since the usual higher water temperature and the low oxygen contents associated with tropical environments result in biased water quality evaluations by this index., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

Sustainable use of groundwater while maintaining economic and social development is a major challenge, and the implementation of wellhead protection areas (WHPA) for public supply wells has been applied as an instrument to overcome it. This study analyzes the WHPA delineation methods: calculated fixed radius (CFR) and two solutions of the WhAEM software (USEPA, 2018), one analytical and one semi-analytical. We compare their results with WHPAs generated by a stochastic three-dimensional MODFLOW-MODPATH model in two scenarios: eight pumping wells operating simultaneously and a single well pumping, both at the same public drinking water supply wellfield located on a coastal plain in Jaguaruna County, south Brazil. For the specific hydrogeological settings, all methods produced satisfactory results when delineating a 50-day time-of-travel (TOT) WHPA for a single well. However, as TOT increases, uncertainties are introduced, and the precision of the results is reduced. Multiple well pumping simultaneously presented similar issues regarding uncertainties caused by three-dimensional flow complexities resulting from well interferences. Despite being the simplest method applied in terms of hydrogeological data needs, the CFR method demonstrated reliability in its results. Additionally, we present an analysis comparing the dimensions of the capture zone with the 10- and 20-year TOT WHPAs, indicating that managing the entire capture zone is the best way to protect groundwater against conservative contaminants. Finally, we compare WHPA generated by a stochastic and a deterministic model to understand how uncertainties can affect model results., (© 2023. The Author(s), under exclusive licence to Springer Nature Switzerland AG.)

This work was conducted at Araxá city, Minas Gerais State, Brazil. The aim was to characterize by different approaches weathering rates at six watersheds occurring there. The study area is well-known in the country due to economic and touristic reasons. Beginning in the 1960's and 1970's, nowadays huge mining activities for niobium and phosphate fertilizer exploitation by different companies are taking place there along with the use of natural mineral waters for health treatment, following a tradition that started in the 19th century for tuberculosis treatment. The dataset utilized in this investigation comprised results obtained in the analysis of distinct geochemical compartments, i.e. rocks, soils, bottom sediments, rainwater and surface waters from small hydrographic basins. The waters of three catchments are extensively used by water-supply systems of Araxá city in order to meet the demand of this resource as a possible supply of drinking water for the local community. Hydrochemical (major and trace constituents) and radionuclides ( 238 U, 234 U, and 210 Po) analyses of rainwater and water bodies samples allowed estimates of the fluxes in each drainage. These fluxes were subtracted from rainfall deposition, yielding positive net values only for bicarbonate and U-isotopes as natural tracers in all watersheds, which allowed to calculate chemical weathering rates of 2.6-38.9 ton/km 2 yr (bicarbonate) and 0.09-19.8 ton/km 2 yr (U-isotopes). Physical weathering rates were obtained from 210 Pb data in bottom sediments and exceeded 200 to 1.3 × 10 5 times the chemical weathering rates evaluated by the U-isotopes approach, a finding compatible with others reported in literature but adopting a diverse conceptual framework. Thus, the development of all analytical protocols along this investigation permitted an integrated appraisal of distinct approaches applied to the same selected site, as well as a comparison of weathering rates with other values reported in the literature, improving the knowledge about this subject in Araxá city watersheds. The novel dataset reported in this paper constitutes an aid to the already existing number of weathering rates elsewhere, helping modellers engaged on predicting future landscape changes., (Copyright © 2022 Elsevier Ltd. All rights reserved.)

Sediment transfer from land to ocean begins in coastal settings and, for large rivers such as the Amazon, has dramatic impacts over thousands of kilometers covering diverse environmental conditions. In the relatively natural Amazon tidal river, combinations of fluvial and marine processes transition toward the ocean, affecting the transport and accumulation of sediment in floodplains and tributary mouths. The enormous discharge of Amazon fresh water causes estuarine processes to occur on the continental shelf, where much sediment accumulation creates a large clinoform structure and where additional sediment accumulates along its shoreward boundary in tidal flats and mangrove forests. Some remaining Amazon sediment is transported beyond the region near the river mouth, and fluvial forces on it diminish. Numerous perturbations to Amazon sediment transport and accumulation occur naturally, but human actions will likely dominate future change, and now is the time to document, understand, and mitigate their impacts.

In this work, a methodology for chemical speciation analysis of inorganic As and Sb in urban dust using slurry sampling and detection by fast sequential hydride generation atomic absorption spectrometry is proposed. Doehlert design and desirability function were used to find the optimum conditions for hydride generation (1.0 mol L -1 HCl and 0.9% m v -1 NaBH 4 ). The accuracy of the analytical method was evaluated by analysis of reference material fly ash (BCR 176R), addition and recovery tests for inorganic As species, and comparison of independent methods for Sb determination in urban dust samples. The determination of the total concentrations of As and Sb and their inorganic species presented good accuracy, between 80 ± 1 and 101 ± 6%. Precision was expressed as the relative standard deviation and was better than 4.7% (n = 3). The limit-of-quantification values were 0.23 and 1.03 mg kg -1 for As and Sb, respectively. The methodology was applied to eight samples of dust collected in an urban area of Salvador and Jaguaquara cities, Bahia, Northeast, Brazil, with an aerodynamic size lower than 38 μm. Concentrations of pentavalent inorganic species (iAs 5+ and iSb 5+ ) in relation to trivalent species (iAs 3+ and iSb 3+ ) were found in urban dust collected in the city of Salvador, which are regarded as more toxic for both elements. The enrichment factor and geoaccumulation index (I geo ) values showed that for some samples, the concentrations of iAs and iSb presented strong enrichment and, and regarding environment, strong to moderately polluted by iAs and iSb, with an indication of anthropogenic contributions. The occurrence of these inorganic constituents in the urban area of Salvador can be related with intense industrial activities and vehicular traffic.

Plastic, as a "flagship species", represents how deeply humans impact the environment. Although scarce, the presence of plastic and other anthropogenic materials in rocks has already been reported in the literature, however, so far, not in the Southern Hemisphere. Thus, the objective of the present study was to report and describe samples of sedimentary rocks containing anthropogenic items cemented with biogenic and siliciclastic material - anthropoquinas - and to discuss implications to the establishment of the Anthropocene and geodiversity conservation. Six samples of anthropoquinas were evaluated, presenting different technofossils (metal bottle caps, ship nail, plastic earring and plastic fragment) and composition (lithic and biogenic fragments). Energy Dispersive X-ray Spectroscopy was conducted on two samples, reflecting differences regarding their genesis. The description of these rocks is concerning and reflects how deeply human behavior influences various natural compartments. Therefore, studies on the effects of marine litter on geodiversity are strongly encouraged., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2020 Elsevier Ltd. All rights reserved.)

The sources and depositional history of polycyclic aromatic hydrocarbons (PAHs) and organochlorine compounds (OCs) over the last century were investigated in sediment cores from the North Adriatic Sea (Po River prodelta) and the South-Western Adriatic Margin (SWAM). Contaminant concentrations were higher in the Po River prodelta. ∑ 16 PAHs ranged from 193 to 533 ng g -1 , ∑ 5 PCBs ranged from 0.9 to 5.2 ng g -1 and ∑DDTs (p,p'-DDD + p,p'-DDE) ranged from 0.1 to 2.5 ng g -1 . In the SWAM, ∑PAHs ranged from 11 to 74 ng g -1 while ∑PCB and ∑DDT concentrations were close to the MQL. Accordingly, contaminant fluxes were much higher in the northern (mean values of 152 ± 31 ng cm 2 y -1 and 0.70 ± 0.35 ng cm 2 y -1 for PAHs and OCs, respectively) than in the southern Adriatic (2.62 ± 0.9 ng cm 2 y -1 and 0.03 ± 0.02 ng cm 2 y -1 for PAHs and OCs, respectively). The historical deposition of PAHs seemed to be influenced by the historical socioeconomic development and by changes in the composition of fossil fuel consumption (from petroleum derivatives to natural gas) in Italy from the end of the 19th century to the present. Similarly, vertical variations in DDT concentrations matched its historical use and consumption in Italy, which started around in the mid-late 1940s to fight typhus during the II World War. Contaminant concentrations detected in sediments does not seem to pose ecotoxicological risk for marine organisms in the Adriatic Sea., (Copyright © 2019. Published by Elsevier Ltd.)

The aim of the present study was to evaluate the presence of polycyclic aromatic hydrocarbons (PAHs) in oysters (Crassostrea rhizophorae) collected from Todos os Santos Bay (Bahia, Brazil). The total PAH concentration was highest in Madre de Deus (36.3 to 37.8 ng g -1 in dry weight, dw), which is located near a petrochemical complex, oil refinery, and commercial port. In the Paraguaçu river estuary, PAH concentrations varied between 23.2 and 25.7 ng g -1 dw. The lowest concentrations (1.55 ng g -1 dw) were found in the Jaguaribe river estuary, which can be considered a relatively preserved area. The main source of PAHs in the study areas was observed to be pyrogenic. Values of benzo[a]pyrene toxic equivalent ranged from 0.28 to 4.20. The concentrations of PAHs in oysters from the Paraguaçu river estuary and in Madre de Deus indicate the possible lifetime risk of developing cancer in humans who feed on it., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

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 'M MAD ' 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 (C deg ), 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 C deg 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.

Freshwater bivalve shell oxygen isotope values ( δ 18 O S ) may act as a recorder of river δ 18 O variations that can then be interpreted in terms of hydrology (e.g. precipitation-evaporation balance, precipitation and river discharge patterns). We investigated the potential of this proxy measured across the hinge of South American unionid shells: Anodontites elongatus collected in Peru and A. trapesialis in Brazil. The isotopic signatures were reproducible between individuals of the same species. A. trapesialis clearly showed a strong δ 18 O S cyclicity in accordance with its growth patterns while A. elongatus presented less clear δ 18 O S with lower amplitude. We confirm that the deposition of successive growth lines and increments is annual, with growth line corresponding to the wet season. Also, we suggest that low amplitude of δ 18 O S in the A. elongatus shells indicates a habitat close to the river while large amplitude of δ 18 O S cycles observed in A. trapesialis shells would reflect a floodplain lake habitat, seasonally disconnected from the river and thus subjected to higher seasonal fluctuations in water δ 18 O. Considering these promising first results, future studies could be directed towards the use of fossil shells to reconstruct the past and present hydrological and geochemical conditions of the Amazon.

The marine environment is constantly being impacted by anthropogenic activities. Nowadays, microplastics (MPs) representing one of the most deleterious material among of all substances and material from anthropogenic origin. The Microplastics (MPs) are particles smaller than 5 mm. This study presents information on abundance, distribution, type and colour of microplastics in the bottom sediments of the continental Shelf of Rio de Janeiro State. This area is strongly impacted due to its location in front of one of the most polluted coastal bays in the Brazilian Coastline. It receives untreated sewage from an Ipanema Beach submarine emissary and also a great amount of sediments dredged from Rio de Janeiro Harbour, which strongly influences the distribution of MPs in the area. The analyses detected the presence of MP in 100% of the samples, composed mainly by secondary microplastics, and almost 50% were fibers, followed by plastic films, plastic fragments and pellets. Based on the nature of the sources of the MP, a great variety of colours was shown, dominated by four main colours: blue, white, transparent, and black, this pattern could potentially increase their bioavailability due to resemblance to prey items, especially to visual raptorial species., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

In this work, fast sequential determination and chemical speciation analysis of inorganic arsenic and antimony in airborne particulate matter collected in outdoor and indoor environments using slurry sampling and detection by hydride generation atomic absorption spectrometry (HG-AAS) is proposed. A Doehlert design was applied to optimise the hydride generation conditions of As and Sb for fast sequential determination in the same aliquot of particulate matter samples after preparation of the slurry. The limits of quantification (LoQ) obtained for As and Sb were 0.3 and 0.9 ng m -3 , respectively. The accuracy of the analytical method was confirmed by analysis of the certified reference material of urban particulate matter (SRM NIST 1648a), presenting concordance with certified values of 92.7±7.7% for As and 91.2±9.5% for Sb. Precision was expressed as relative standard deviation (% RSD, n=3), with our results presenting values better than 3.4% and 4.2% for total inorganic As and Sb, respectively. For all analysed samples, total As concentrations and its inorganic species were below the LoQ of the analytical method (<0.3 ng m -3 ). However, the averages of total inorganic Sb concentrations in airborne particulate matter, collected as total suspended outdoor particles (TSP outdoor ), inhalable particulate matter (PM 10 ), and total suspended indoor particles (TSP indoor ), were 3.1±0.5, 2.4±0.6, and 2.6±0.4 ng m -3 , respectively. Trivalent Sb (Sb 3+ ) was the predominant inorganic species in all samples investigated, with mean percentages of 76%, 72%, and 73% in TSP outdoor , PM 10 , and TSP indoor , respectively. The presence of Sb and its predominant inorganic form (Sb 3+ ) can be attributed to vehicular traffic close to the sampled urban areas. Therefore, fast sequential determination of As and Sb and their inorganic species in particulate matter samples prepared as slurry by FS-HG-AAS is an efficient, accurate, and precise method and can be successfully applied to routine analysis.

Microplastics are important vectors for the transport and accumulation of persistent organic contaminants in coastal and marine environments. We determined the concentration of polycyclic aromatic hydrocarbons (PAHs) and polychlorinated biphenyls (PCBs) associated with microplastic pellets collected along a 39-km stretch of Brazil's South Atlantic coastline to understand the spatial dynamics and potential risk posed by these contaminants. Total PAH concentrations ranged from 1,454 to 6,002 ng g -1 and regularly exceeded the threshold effect level (TEL) for sediments defined by the United States Environmental Protection Agency. Sampling stations, spaced evenly along the coastline (i.e., 3-km intervals) exhibited a general north-to-south decline in the concentrations of some PAHs, but this spatial gradient was complicated by small-scale differences in the concentrations and composition of associated contaminants. Similarly, analysis of individual isomer ratios revealed further complexity driven by differences in the contribution of petrogenic versus pyrolytic inputs which pose different levels of risk to marine organisms. PCB concentrations ranged from 0.8 to 104.6 ng g -1 and were dominated by low chlorinated congeners likely to have originated from major industrial areas to the north. Overall, this study highlights the challenge of directly linking microplastic pollution with the potential toxicological effects of organic contaminants in coastal waters. We recommend that monitoring programs should explicitly consider both the origin (i.e., pellet sources and dispersal pathways) and nature of organic contamination (i.e., concentration and composition) when assessing the risks for biota and human health., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Oil exploitation, the basis of the world energy sector, is linked to risks and accidents, causing damage to the affected regions. Oil-suspended particulate matter aggregate (OSA) is a promising technology to mitigate those effects. The present study periodically (February 2016 and July 2016) evaluated the dispersion of oil at 28 points in the São Paulo River's estuary, Todos os Santos Bay, Brazil, analyzing the influence of suspended particulate matter (SPM), particulate organic carbon (POC), ions, and chlorophyll on the formation OSA, targeting the prediction of possible ecotoxicological risks. The results showed that the estuary presented similar characteristics in the expeditions, reflecting the oil dispersion pattern through the formation of OSAs, being 92.86% dispersed in the column in the first and 85.71% in the second expedition. The results also pointed to the possibility of pollution in the food chain, reduced fertility, the emergence of abnormalities and the gradual disappearance of species across the whole river in a possible oil spill.

Characterized by fluvio-alluvial sedimentation processes, the heterogeneity in the Pantanal Basin allows its division in several sub-regions, which present natural characteristics of their own. It is possible to find in the literature different proposals to subdivide the Pantanal plain, which vary in total area and number of sub-regions. Each author uses specific criteria - mainly vegetation, soil and humidity - in his delimitation, but does not consider the tectonic aspects of the basin. In this sense, we intend to analyze three Pantanal delimitations from the literature and to relate them to the neotectonic context of the Pantanal plain by comparing the boundaries proposed in the delimitations to structural lineaments present in the basin. As a result, we observe that the comparison of the Pantanal boundaries with the lineaments shows a high compatibility between them, suggesting the influence of these structures in the development of the sub-regions.

Poultry litter is widely used as fertilizer in soils and can be a relevant source of heavy metals for agricultural environments. In this study, poultry litter fertilization of long-term (< 1-30 years) was evaluated in tropical soils. Our main goal was to investigate the occurrence of temporal variation in the available fraction of heavy metals (Cu, Cr, Zn, Pb, Cd, and Mn) in soils, in addition to their environmental loads through new indexes for risk assessment. The highest mean concentrations in poultry litter were the following: 525 mg kg -1 for Mn, 146 mg kg -1 for Zn, and 94.4 mg kg -1 for Cu. For soils, concentrations were higher for the same heavy metals: Mn (906 mg kg -1 ), Zn (111 mg kg -1 ), and Cu (26.3 mg kg -1 ). Significant accumulation (p < 0.05) in fertilized soils was observed for Cu, Cr, and Zn. The high estimates of poultry litter input based on geological background (LI GB ) for Cu, Cr, and Zn coincided with the accumulation observed in soils, confirming the effectiveness of the index. The risk of biogeochemical transfer based on fertilized soils (LI FS ) decreased for Cu, Cr, and Zn between 10 and 30 years of soil fertilization. For Mn, a very high LI FS was estimated in all long-term fertilized soils. The proposed indices, based on heavy metal concentration, can be used in risk assessments to guide future studies that analyze other environmental matrices possibly impacted by manure and poultry litter fertilization.

Three-stage sequential extraction BCR was applied to surface sediments from the west part of Guanabara Bay to assess the mobility of Zn, Cu, Pb, Ni, Cr, and Mn. Results were satisfactory for the analysis of certificate standard material (BCR 701), with recoveries between 71 (Cu) and 123% (Cr). Evaluation of organic matter composition classified the area as eutrophic (CHO:PRT > 1), with aged organic detritus at some stations. Zn exhibited by far the greatest bioavailability, with 43.49% of its concentrations associated with the exchangeable fraction. Cu and Cr showed stronger affinity for organic matter, with 51.18 and 48.73% of their concentrations, respectively, bounded to the oxidizable fraction. Pb presented higher concentrations in the reducible fraction (45.41%). The strongest lithogenic contribution was shown by Ni (31.91%) and Mn (35.44%). PCA clearly showed the determinant role of organic matter and fine sediments in the distribution of metals in the study area and also a common source for these elements, with the exception of Cu. Risk Assessment Code (RAC) established Zn as the most concerning element in the study area. The decreasing mobility order, based on the sum of the three extractable fractions of BCR, was Pb > Cu > Cr > Zn > Ni > Mn. The comparison of the results with sediments quality guidelines (SQG) proved fractionation to be mandatory in the evaluation of effective ecological risk concerning trace elements in sediments.

The atmospheric dispersion atmospheric plume of the metropolitan region and neighborhoods of the city of Rio de Janeiro was investigated through elemental analyzes (Na, K, Al, Mn, Pb, Ni, Cr) and stable lead isotopes in two epiphytes; the lichen Parmotrema crinitum (Ach.) and the bromeliad Tillandsia usneoides (L.). All the elements had lower concentrations in epiphytes than in rocks of the local geological basement, with the exception of K, which was similar to rocks. This behavior was attributed to the nutritional essentiality and abundance of this element in the environment. The concentrations of Na, Pb and the 206Pb/207Pb and 208Pb/206Pb ratios indicated the presence of spatial gradients in the path (a) sea shore → continent, and (b) urban center → farmlands. These patterns were associated with the mesoscale atmospheric circulation regime, in which, during the arrival of cold fronts, air masses from the metropolitan region of Rio de Janeiro are transported towards the mountainous region of Teresópolis, which acts as a barrier to the dispersion of pollutants. The bromeliad Tillandsia usneoides and the lichen Parmotrema crinitum were linked to Na and Pb atmospheric levels, respectively.

The objective of this study was to analyze spatial-seasonal changes to identify the natural and anthropic processes that control groundwater hydrogeochemistry in urban aquifers in municipality of Lençóis (Bahia). Tourism is the main activity of this municipality, which is an important tourist destination in northeastern Brazil and which maintains its tourism infrastructure by using groundwater. Two field campaigns were conducted (dry and rainy seasons) in order to collect groundwater samples extracted from 15 tubular wells distributed over the urban area of the municipality. The Piper diagram, multivariate statistical analyses, and artificial neural networks indicated that there are two types of water (Na-Cl and Na-[Formula: see text] - ), which were divided into five different clusters. Seasonal variation was observed to significantly alter groundwater hydrogeochemistry. According to the Gibbs diagram, groundwater within the urban area of Lençóis belonged to the rainfall dominance, demonstrating low water-rock interaction. Hydrogeochemical modeling results suggested hydrolysis as the main natural factors controlling process. However, mineral dissolution also occurred in one of the clusters. Human-originated trace contamination by nitrate, chloride, and sulfate occurred in a zone of the urban area. This contamination was observed regardless of climate seasonality, indicating that the main controlling process for groundwater hydrochemistry in this region is wastewater mobilization (indirect artificial recharge).

Fluctuations of environmental factors in intertidal habitats can disrupt the trophic balance of mixotrophic cnidarians. We investigated the effect of tidal environments (subtidal, tidal pools and emerged areas) on fatty acid (FA) content of Zoanthus sociatus and Siderastrea stellata. Effect on photophysiology was also accessed as an autotrophy proxy. There was a general tendency of a lower percentage of zooplankton-associated FAs in colonies from emerged areas or tidal pools when compared with colonies from the subtidal environment. Moreover, tidal environment significantly affected the photophysiology of both species. Colonies from the subtidal generally showed lower values of α, ETR max and E k when compared with their conspecifics from tidal pools or emerged areas. However, the absence of consistent patterns in F v /F m and in dinoflagellate-associated FAs, suggest that these corals are well adapted to intertidal conditions. This suggests that intertidal pressures may disturb the trophic balance, mainly by affecting heterotrophy of these species., (Copyright © 2018 Elsevier Ltd. All rights reserved.)

The sources and depositional history of OCPs (organochlorine pesticides), PCBs (polychlorinated biphenyls) and PAHs (polycyclic aromatic hydrocarbons) over the last 100years were determined in two sediment cores collected in the Amazon region. It was possible to distinguish two depositional periods along the cores. The first period occurred before extensive anthropogenic effects were registered in the sediments. During this time interval, the concentrations of all OCPs and PCBs were below the detection limits (DL), and the PAH concentrations were low and essentially constant (58.19-124.28ngg -1 ). The second period starts in the mid-1960s and reflects the increased human influence in the area. The concentrations of OCPs, PCBs, and PAHs increased towards the top of the cores, varying between

-1 ,

-1 and 331 to 2341ngg -1 , respectively. In general, OCP results showed trends corresponding to the production, usage and prohibition periods of POPs in Brazil. Compounds related to wood treatment, such HCHs and chlordanes, were predominant among the OCPs, which may be associated with many sawmills located in this region. The increase in PAH concentration after the 1960s is mainly due to forest fires, caused by the implementation of large-scale cattle ranches, which burned forests to create pastures. The background PAH concentrations before the 1960s are probably related to natural diagenetic processes., (Copyright © 2017 Elsevier B.V. All rights reserved.)

Samples of one lichen species, Parmotrema crinitum, and one bromeliad species, Tillandsia usneoides, were collected in the state of Rio de Janeiro, Brazil, at four sites differently affected by anthropogenic pollution. The concentrations of aluminum, cadmium, copper, iron, lanthanum, lead, sulfur, titanium, zinc, and zirconium were determined by inductively coupled plasma-atomic emission spectroscopy. The environmental diagnosis was established by examining compositional changes via perturbation vectors, an underused family of methods designed to circumvent the problem of closure in any compositional dataset. The perturbation vectors between the reference site and the other three sites were similar for both species, although body concentration levels were different. At each site, perturbation vectors between lichens and bromeliads were approximately the same, whatever the local pollution level. It should thus be possible to combine these organisms, though physiologically different, for air quality surveys, after making all results comparable with appropriate correction. The use of perturbation vectors seems particularly suitable for assessing pollution level by biomonitoring, and for many frequently met situations in environmental geochemistry, where elemental ratios are more relevant than absolute concentrations.

The toxic metal lead (Pb) can be harmful to human health in various manners, but is also considered as a distinguished tracer of environmental pollution since the relative abundance of its four stable isotopes with the atomic masses of 204, 206, 207, and 208 varies with the emission source. This study is focused on the Pb concentrations and isotope ratios in the particulate matter of the Brazilian city of Goiânia in order to determine the main Pb emission sources. Particulate matter samples were collected on clean Teflon filters during rainy and dry season in 2014 in the center of Goiânia city near main roads with a high traffic volume. Pb concentrations as well as stable Pb isotope ratios of the particulate matter samples were analyzed by inductively coupled plasma-mass spectrometry. To apply this analytical technique successfully, it was necessary to optimize parameters in case of acquisition time, detector dead time, and mass discrimination, which affect the measurement accuracy and precision. Results showed that Pb concentrations in Goiânia were different between rainy and dry season. Pb concentrations showed higher values and less variation in dry season than in rainy season. Pb isotope ratios demonstrated significant variations between dry and rainy season. An enrichment of 206 Pb isotopes related to 207 Pb and 208 Pb isotopes was observed in dry season. However, the comparison of the obtained isotopic Pb signature with data of potential Pb sources from previous studies indicated that traffic-related sources should be considered as main Pb source in the particulate matter of Goiânia. These assumptions were incorporated by the calculation of the contribution factor of Pb coming from traffic-related sources by applying binary mixing equations.

The application of zinc (Zn) isotopes in bivalve tissues to identify zinc sources in estuaries was critically assessed. We determined the zinc isotope composition of mollusks (Crassostrea brasiliana and Perna perna) and suspended particulate matter (SPM) in a tropical estuary (Sepetiba Bay, Brazil) historically impacted by metallurgical activities. The zinc isotope systematics of the SPM was in line with mixing of zinc derived from fluvial material and from metallurgical activities. In contrast, source mixing alone cannot account for the isotope ratios observed in the bivalves, which are significantly lighter in the contaminated metallurgical zone (δ 66 Zn JMC  = +0.49 ± 0.06‰, 2σ, n = 3) compared to sampling locations outside (δ 66 Zn JMC  = +0.83 ± 0.10‰, 2σ, n = 22). This observation suggests that additional factors such as speciation, bioavailability and bioaccumulation pathways (via solution or particulate matter) influence the zinc isotope composition of bivalves., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

This study was carried out to evaluate the concentration of trace elements (As, Cd, Cu, Pb, and Zn) in the muscle of carnivorous fish species from three different areas of Todos os Santos Bay (BTS), Bahia State, Brazil. Trace elements were analyzed using inductively coupled plasma-optical emission spectrometry (ICP-OES), and consumption rates advisory for minimizing chronic systemic effects in children and adults were estimated. As concentrations in fish samples from Jiribatuba were higher than legal limits set by FAO, and Cd concentrations in fish from Iguape Bay were high in comparison with FAO and EC. This study provides information about the fish consumption limits, considering the elements concentrations observed in the analyses, in particular As and Cd, necessary for minimizing potential health risks.

In this study, an analysis was performed on the concentrations of the trace elements Al, As, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, V, and Zn in muscle of two carnivorous and one planktivorous fish species collected at Todos os Santos Bay (BTS). The accumulation order of the trace elements in Lutjanus analis was Al >Zn >Fe >Cr >Ba >Ni. In Cetengraulis edentulus, the order was Al >Fe >Zn >Cr >Ni >Mn >As. In the species Diapterus rhombeus, the order was Al >Fe >Zn >Cr >Ni >Mn >Cd. To determine the risk related to the consumption of fish, toxicity guidelines were used as standard references. It was observed that the species C. edentulus contained concentrations of As exceeding WHO limits, but these concentrations were acceptable according to the Agência Nacional de Vigilância Sanitária (ANVISA) guidelines. Cd levels were found only in D. rhombeus and in low concentrations according to the determinations of WHO and ANVISA. Pb levels were not detected in any of the three fish species. The analyzed elements did not differ statistically according to the species and feeding habits. The results point to possible risks of human contamination by As related to the consumption of the fish species C. edentulus from the BTS.

We reveal a dose-response relationship for bioaccumulation of Zn, Cu and Cr in shrimp Litopenaeus schmitti from Sepetiba Bay, Rio de Janeiro, Brazil. Our model estimates the current risk (AD 50 was 70% of the legal limit) and the daily metal uptake rate for each metal. It can also evaluate the relative reliability of predictions for tissue concentrations reaching the legal limits for human consumption (approximately 1year) and predictions related to asymptotic length, arising from (i) direct regression of the metal concentration (MeC) versus total length (TL) and age (duration of exposure), and (ii) correlation of the incorporation rate (IR=MeC/TL) with age. Metal incorporation rates (IR), i.e. a kinetic proxy for absorption during growth up to attainment of asymptotic length, decrease with age, reflecting a slow-down in metal absorption. This pattern mitigates the high initial concentrations observed for juveniles., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

For experiments concerning the formation of oil-suspended particulate matter (SPM) aggregates (OSA), oil and sediment samples were collected from Campos Basin and six stations of Paraguaçu estuary, Todos os Santos Bay, Brazil, respectively. The sediments samples were analyzed for organic matter determined by the EMBRAPA method, nitrogen determined by the Kjeldahl method, and phosphorus determined by the method described by Aspila. The oil trapped in OSA was extracted following the method described by Moreira. The experiment showed a relationship between the amount of organic matter and OSA formation and consequently the dispersion of the studied oil. On the basis of the buoyancy of OSA and the ecotoxicological effects on pelagic and benthic community, the priority areas for application of remediation techniques are Cachoeira, Maragogipe, and Salinas da Margarida because of the large amount of oil that accumulated at the bottom of the experiment flask (5.85%, 27.95%, and 38,98%; 4.2%, 17.66%, and 32.64%; and 11.82%, 8.07%, and 10.91% respectively)., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Total concentrations of Ni, Cr, Cu, Pb and Zn were determined in surface sediments from 30 stations in Guanabara Bay in 1999 and 2008. An approach using various environmental indices was used to assess contamination status of metals. This approach allowed the comparison with different coastal areas. Background Enrichment Index, Contamination index and Ecological Risk index (Pollution Load Index; Sediment Quality Guideline Quotient and Ecological Risk Index) were calculated for the metals. Results revealed a great load of organic matter and significant increases in Cu and Pb levels between 1999 and 2008. The concentrations of Cr and Zn were of great concern, surpassing the values of Probable Effect Level reference values. In spite of the differences of each index, results effectively revealed the striking contamination in Guanabara Bay concerning trace metals, and also suggested potential risk to local biota. The contamination of the northwest area was notably higher than the rest of the bay. In comparison with some other coastal bays around the world, Guanabara Bay stood out as a remarkably contaminated environment., (Copyright © 2016 Elsevier Inc. All rights reserved.)

Approximately 40% of the volume of domestic sewage generated in the São Paulo State is untreated and released into water bodies, causing serious pollution problems that affect the water quality and especially the suspended sediments transported by rivers. Thus, this paper investigates the seasonal influence on the origin and fluxes of Cu, Co, Cr, Zn, Cd, Ni, Sc and particulate organic matter (POM) in sediments transported by a disturbed watershed in the São Paulo State, i.e. the Sorocaba River basin. POM was characterized using particulate organic carbon, particulate organic nitrogen, C:N ratio and δ 13 C and δ 15 N stable isotopic composition. Eight sample collections of fine suspended sediments (FSS) were carried out at the mouth of the Sorocaba River from July 2009 to May 2010. During the study period, the discharge rate followed the seasonal variation trend of the past 25 years. Zn was the most abundant trace element in the FSS, followed by Cr, Cu, Ni, Co, Sc and Cd. There was a higher concentration of trace elements during the dry season, except for Sc and Co, which did not vary seasonally. The POM showed the same trend, with higher concentrations during the dry season. The calculated enrichment factors and geoaccumulation index indicated that most of the trace elements are of geogenic origin, except for Zn, which showed significant anthropogenic contributions (55%). The elemental and isotopic analysis of C and N and C:N ratio indicated that the anthropogenic origin of POM found in the FSS is related mainly to domestic sewage (97%), while the significant correlation found between the concentrations of Zn and POM indicates that the main anthropogenic source of Zn is related to this domestic sewage. The FSS load transported during the study period was of 373,194 t y -1 , of which 87% occurred during the rainy season., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Floating litter in the estuarine system of Santos-São Vicente is common and is part of day-to-day activities of various users of the area. The objective of the present study was to carry out a quali-quantitative evaluation of the occurrence of floating litter, to infer their sources, and to identify environmental factors that are likely to control occurrence and distribution, with particular emphasis on the effects of tidal regimes. Six sampling stations were selected along the aforementioned estuary and visited monthly between July 2010 and January 2012. Floating litter was counted from a fixed sampling station. Plastics prevailed (89.64%) and their main source was domestic activities (55.41%). More litter was found during ebb spring tides, with higher concentrations obeying confluence patterns of the estuary's channels. Results indicated that occurrence can be attributed to the deficiency in basic sewage system in the area and the deliberate disposal into the estuary by the local population., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Effects of acid mine drainage (AMD) were investigated in surface waters (Laranjinha River and Ribeirão das Pedras stream) and groundwaters from a coal mining area sampled in two different seasons at Figueira city, Paraná State, Brazil. The spatial data distribution indicated that the acid effluents favor the chemical elements leaching and transport from the tailings pile into the superficial water bodies or aquifers, modifying their quality. The acid groundwaters in both sampling periods (dry: pH 2.94-6.04; rainy: pH 3.25-6.63) were probably due to the AMD generation and infiltration, after the oxidation of sulfide minerals. Such acid effluents cause an increase of the solubilization rate of metals, mainly iron and aluminum, contributing to both groundwater and surface water contamination. Sulfate in high levels is a result of waters' pollution due to AMD. In some cases, high sulfate and low iron contents, associated with less acidic pH values, could indicate that AMD, previously generated, is nowadays being neutralized. The chemistry of the waters affected by AMD is controlled by the pH, sulfide minerals' oxidation, oxygen, iron content, and microbial activity. It is also influenced by seasonal variations that allow the occurrence of dissolution processes and the concentration of some chemical elements. Under the perspective of the waters' quality evaluation, the parameters such as conductivity, dissolved sodium, and sulfate concentrations acted as AMD indicators of groundwaters and surface waters affected by acid effluents.

Various mineral processing operations to produce pure metals from mineral ores generate sludges, residues, and other unwanted by-products/wastes. As a general practice, these wastes are either stored in a reservoir or disposed in the surrounding of mining/smelting areas, which might cause adverse environmental impacts. Therefore, it is important to understand the various characteristics like heavy metal leaching features and potential toxicity of these metallurgical wastes. In this study, zinc plant leach residues (ZLRs) were collected from a currently operating Zn metallurgical industry located in Minas Gerais (Brazil) and investigated for their potential toxicity, fractionation, and leachability. Three different ZLR samples (ZLR1, ZLR2, and ZLR3) were collected, based on their age of production and deposition. They mainly consisted of Fe (6-11.5 %), Zn (2.5 to 5.0 %), and Pb (1.5 to 2.5 %) and minor concentrations of Al, Cd, Cu, and Mn, depending on the sample age. Toxicity Characteristic Leaching Procedure (TCLP) results revealed that these wastes are hazardous for the environment. Accelerated Community Bureau of Reference (BCR) sequential extraction clearly showed that potentially toxic heavy metals such as Cd, Cu, Pb, and Zn can be released into the environment in high quantities under mild acidic conditions. The results of the liquid-solid partitioning as a function of pH showed that pH plays an important role in the leachability of metals from these residues. At low pH (pH 2.5), high concentrations of metals can be leached: 67, 25, and 7 % of Zn can be leached from leach residues ZLR1, ZLR2, and ZLR3, respectively. The release of metals decreased with increasing pH. Geochemical modeling of the pH-dependent leaching was also performed to determine which geochemical process controls the leachability/solubility of the heavy metals. This study showed that the studied ZLRs contain significant concentrations of non-residual extractable fractions of Zn and can be seen as a potential secondary resource for Zn.

Potential toxicity of sedimentary Cu, Zn and Pb were evaluated based on their fractionation at the inner part of Jurujuba, a small sound at the eastern margin of Guanabara Bay, Rio de Janeiro. Biogeochemical composition revealed an environment extremely enriched with anthropic organic matter and characterized as a detrital heterotrophic system. The fractionation analysis showed that Pb exhibited more affinity with the residual fraction followed by the amorphous Fe/Mn fraction. Cu and Zn were more expressive in the amorphous Fe/Mn fraction followed by the organic one and crystalline Fe/Mn fraction, respectively. According to Igeo index, sediments proved to be highly polluted by Zn and Cu and moderated polluted by Pb. Despite the actual contamination of Jurujuba sediments, the mobility of these elements seems to be limited since the most excessive concentrations were found in the less available fractions, depending on extreme physico-chemical variations to be released., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

This paper reports the bioavailability of the metals (cadmium, copper, zinc, lead, and nickel) in sediment samples collected in seven stations from the São Paulo Estuary, Todos os Santos Bay, Brazil. The bioavailability was determined by employing the technique "acid-volatile sulfide (AVS) and simultaneously extracted metal (SEM)". The elements cadmium, copper, lead, and zinc were determined using differential pulse anodic stripping voltammetry (DPASV), while nickel was quantified utilizing electrothermal atomic absorption spectrometry (ET AAS). The accuracy of these methods was confirmed using a certified reference material of estuarine sediment (NIST 1646). The sulfide was quantified using potentiometry with selective electrode and the organic matter determination employing an indirect volumetric method using potassium dichromate and iron(II) sulfate solutions. The bioavailability of the metals was estimated by relationship between the concentration of AVS and the sum of the concentrations of the simultaneously extracted metals (ΣSEM), considering a significant toxicity when (ΣSEM)/(AVS) is higher than 1. The bioavailability values in the seven stations studied varied from 0.93 to 1.31 (June, 2014) and from 0.34 to 0.58 (September, 2014). These results demonstrated a critical condition of toxicity (bioavailability >1) in six of the seven sediment samples collected during the rainy season (June, 2014). In the other period (September, 2014), the bioavailability was always lower than 1 for all sediment samples collected in the seven stations. The individual values of the concentrations of the five metals were compared with the parameters PEL (probable effects level) and TEL (threshold effects level), which are commonly employed for characterization of ecological risk in environmental systems. This comparison revealed that all metals have concentrations lower than the PEL and only zinc and lead in some stations have contents higher than the TEL. The bioavailability evaluation and the concentrations achieved for the five elements in the sediments samples analyzed demonstrated that the ecosystem studied does not present an environmental risk.

Saccharomyces cerevisiae immobilized in agarose gel as binding phase and polyacrylamide as diffusive layer in the diffusive gradient in thin films technique (DGT) was used for selective determination of methylmercury (MeHg). Deployment tests showed good linearity in mass uptake up to 48 h (3276 ng). When coupling the DGT technique with Cold Vapor Atomic Fluorescence Spectrometry, the method has a limit of detection of 0.44 ng L(-1) (pre concentration factor of 11 for 48 h deployment). Diffusion coefficient of 7.03 ± 0.77 × 10(-6) cm(2) s(-1) at 23 °C in polyacrylamide gel (pH = 5.5 and ionic strength = 0.05 mol L(-1) NaCl) was obtained. Influence of ionic strength (from 0.0005 mol L(-1) to 0.1 mol L(-1) NaCl) and pH (from 3.5 to 8.5) on MeHg uptake were evaluated. For these range, recoveries of 84-105% and 84-98% were obtained for ionic strength and pH respectively. Potential interference due to presence of Cu, Fe, Mn, Zn was also assessed showing good recoveries (70-87%). The selectivity of the proposed approach was tested by deployments in solutions containing MeHg and Hg(II). Results obtained showed recoveries of 102-115 % for MeHg, while the uptake of Hg(II) was insignificant. The proposed approach was successfully employed for in situ measurements in the Negro River (Manaus-AM, Brazil)., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Tributyltin (TBT) contamination is still recorded in the environment even after its ban in antifouling paints. Since most biomonitors of TBT contamination, through imposex evaluation, are hard-bottom gastropods, the identification of soft-bottom sentinels has become useful for regions where rocky shores and coral reefs are absent. Thus, an evaluation of Olivella minuta and Hastula cinerea as monitors of TBT contamination was performed in two sandy beaches located under influence area of São Sebastião harbor (São Paulo state, Brazil), where previous and simultaneous studies have reported environmental contamination by TBT. In addition, the imposex occurrence in H. cinerea was assessed in an area with low marine traffic (Una beach), also located in São Paulo State. A moderate imposex incidence in O. minuta was detected in Pernambuco (% I = 9.36, RPLI = 4.49 and RPLIstand = 4.27) and Barequeçaba (% I = 2.42, RPLI = 0.36 and RPLIstand = 0.81) beaches, indicating TBT contamination. In contrast, more severe levels of imposex were recorded for H. cinerea in Una beach (% I = 12.45) and mainly in Barequeçaba beach (% I = 98.92, RPLI = 26.65). Our results suggest that O. minuta and H. cinerea have good potential as biomonitors for TBT based on their wide geographical distribution, common occurrence in different coastal sediment habitats, easy collection, and association with TBT-contaminated sediments.

The Cerrado is a biome in Brazil that is experiencing the most rapid loss in natural vegetation. The objective of this study was to analyze the changes in the spectral response in the red, near infrared (NIR), middle infrared (MIR), and normalized difference vegetation index (NDVI) when native vegetation in the Cerrado is deforested. The test sites were regions of the Cerrado located in the states of Bahia, Minas Gerais, and Mato Grosso. For each region, a pair of Landsat Thematic Mapper (TM) scenes from 2008 (before deforestation) and 2009 (after deforestation) was compared. A set of 1,380 samples of deforested polygons and an equal number of samples of native vegetation have their spectral properties statistically analyzed. The accuracy of deforestation detections was also evaluated using high spatial resolution imagery. Results showed that the spectral data of deforested areas and their corresponding native vegetation were statistically different. The red band showed the highest difference between the reflectance data from deforested areas and native vegetation, while the NIR band showed the lowest difference. A consistent pattern of spectral change when native vegetation in the Cerrado is deforested was identified regardless of the location in the biome. The overall accuracy of deforestation detections was 97.75%. Considering both the marked pattern of spectral changes and the high deforestation detection accuracy, this study suggests that deforestation in Cerrado can be accurately monitored, but a strong seasonal and spatial variability of spectral changes might be expected.

The degree of pyritization (DOP) and the extension of metals incorporation into pyrite was investigated at Guanabara Bay sediments. Maximum concentrations of total organic carbon (TOC), total sulfur, biopolymers and viable bacteria cells were observed in silted stations close to discharge points of sewage and minimum concentrations at sandy stations at the entrance of the bay. Pyrite iron concentrations (Fepy) was always lower than the reactive iron and Fepy were below the detection limit at sandy stations. The same trend was found to metals, which its degree of pyritization was Mn=Cu>As=Co>Ni>Cd>Zn≫Pb>Cr. The bay gathers all required factors to sulfate reduction and pyrite formation, once the C:S ratio express the reduced tendency conditions, almost half of the TOC present in its sediments is labile and both reactive sulfur and iron are available. However the degree of trace metals pyritization did not exceed 20%, consistent with the median DOP (29%)., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

In this work, a device based on diffusive gradients in thin films (DGT) was evaluated for the determination of Hg(II) in river water. The DGT device was assembled with a cellulose phosphate ion exchange membrane (P81 Whatman) as a binding phase and agarose gel 1.5% (m/v) as a diffusive layer. Laboratory deployments showed that the binding of Hg(2+) ([Hg(DGT)]/[Hg(solution)]) by P81 membrane was more effective (97%) than the Chelex 100 resin (80%).The effect of ionic strength, pH and potential interfering ions on Hg binding with DGT׳s was investigated. The results showed no significant effect on the binding of Hg(II) at pH range from 3.5 to 8.5 and at an ionic strength range from 0.0005 to 0.1 mol L(-1). Uptakes of 50 µg L(-1) Hg(II) by P81 membrane were not affected by Fe, Mn, Zn, Cu, Ca and Mg at the concentration range of 200-1800 µg L(-1). Finally, the DGT device using the P81 as the binding layer was applied for in situ measurements of Hg in river water. For in situ measurements, the labile Hg concentration (from <2 to 13 ng L(-1)) was lower than 10% of the dissolved fraction (from 155 to 446 ng L(-1))., (Copyright © 2014 Elsevier B.V. All rights reserved.)