Alternatives to 137Cs for 210Pb dating validation in south America and in the Carribean region: Point and diffuse sources.

As today the 137Cs fallout peak, in sediment cores, corresponds only to 25% of its initial concentration, alternatives to the use of 137Cs as a210Pb sediment dating validation tool are proposed. In highly industrialized bays, such as Guanabara Bay in the Rio de Janeiro metropolitan region, several chemical/compounds from the surrounding industry releases may be applied as validation tools. Chromium and copper profiles in a sediment core adequately fit the expected pattern due to the implementation of a chemical plant in 1958, reaching their maximum discharge in 1982 and subsequently decreasing due to the operation of a new wastewater treatment plant. A diffuse source such, as the PCB-based mixture Askarel, was also applied as an alternative validation tool, and the observed concentration profile reproduced the expected behavior, with increasing concentration after the Second World War and a decrease after the ban of this product in 1981. The observed Aroclor 1254 and 1260 mixture chlorination rates fit the most widely distributed PCB-based products in the country.

Ecotoxicological assessments of atmospheric biomonitors exposed to urban pollution in a Brazilian metropolis.

Subcellular metal distribution assessments are the most adequate biomonitoring approach to evaluate metal toxicity, instead of total metal assessments This study aimed to assess subcellular metal distributions and associations to the main metal exposure biomarker, metallothionein (MT), in two bromeliad species (Tillandsia usneoides and Tillandsia stricta) exposed established in industrial, urban, and port areas in the metropolitan region of Rio de Janeiro, southeastern Brazil, through an active biomonitoring approach conducted one year. Metals and metalloids in three subcellular fractions (insoluble, thermolabile and thermostable) obtained from the MT purification process were determined by inductively coupled plasma mass spectrometry (ICP-MS). Lower MT concentrations were observed both during the dry sampling periods, associated to the crassulacean acid metabolism (CAM) and during the COVID-19 pandemic, due to reduced urban mobility, decreasing pollutant emissions. The percentage of non-bioavailable metals detected in the insoluble fraction increased throughout the sampling period for both species. Several metals (Cr, Co, Cu, Cd, Mn, Ni, Se, and Zn), most associated with vehicle emissions, the main pollutant source in urban centers, were detected in the thermostable fraction and are, thus, associated with MT through the MT-metal detoxification route. Insoluble metal concentrations were higher in T. stricta, indicating that this species seems less susceptible to cellular metal exposure damage. A potential protective effect of Se and Fe was detected against Pb, suggested by a strong negative correlation, which may be attributed to antioxidant roles and similar uptake routes, respectively.

Assessing over decadal biomass burning influence on particulate matter composition in subequatorial Amazon: literature review, remote sensing, chemical speciation and machine learning application.

A study on aerosols in the Brazilian subequatorial Amazon region, Tangará da Serra (TS) and Alta Floresta (AF) was conducted and compared to findings in an additional site with background characteristics (Manaus, AM). TS and AF counties suffer from intense biomass burning periods in the dry season, and it accounts for high levels of particles in the atmosphere. Chemical characterization of fine and coarse particulate matter (PM) was performed to quantify water-soluble ions (WSI) and black carbon (BC). The importance of explanatory variables was assessed using three machine learning techniques. Average concentrations of PM in AF and TS were similar (PM2.0, 17±10 µg m-3 (AF) and 16±11 µg m-3 (TS) and PM10-2.0, 13±5 µg m-3 (AF) and 11±7 µg m-3 (TS)), but higher than the background site. BC and SO4 2- were the prevalent components as they represented 27%-68% of particulates chemical composition. The combination of the machine learning techniques provided a further understanding of the pathways for PM concentration variability, and the results highlighted the influence of biomass burning for key sample groups and periods. PM2.0, BC, and most WSI presented higher concentrations in the dry season, providing further support for the influence of biomass burning.

Risk of Collapse in Water Quality in the Guandu River (Rio de Janeiro, Brazil).

The Guandu River, one of the main rivers in the state of Rio de Janeiro, provides water for more than nine million people in the metropolitan region. However, the Guandu has suffered from massive domestic and industrial pollution for more than two decades, leading to high levels of dissolved total phosphorus, cyanobacteria, and enteric bacteria observed during the summers of 2020 and 2021. The use of Phoslock, a palliative compound, was not effective in mitigating the levels of phosphorus in the Guandu River. Furthermore, potable water driven from the river had levels of 2-MIB/geosmin and a mud smell/taste. With all these problems, several solutions are proposed for improving the Guandu River water quality, including establishment of (i) sewage treatment plants (STPs), (ii) strict water quality monitoring, (iii) environmental recovery (e.g., reforestation), and (iv) permanent protected areas. The objective of this paper is to verify the poor water quality in the Guandu and the ineffectiveness and undesired effects of Phoslock.

Historic variation of trace elements in pinnipeds with spatially segregated trophic habits reveals differences in exposure to pollution.

Marine mammals and the ecological functions they provide to coastal and pelagic ecosystems are increasingly threatened by the intensification of anthropogenic impacts. The Uruguayan coastline throughout the 20th century, like other coastal environments worldwide, has been the sink of a variety of trace metals derived from the rapid urbanization and industrialization of related land areas. This coastline is inhabited by two species of pinnipeds trophically and spatially segregated. Otaria byronia feeds in coastal environments while Arctocephalus australis preys mainly offshore. The present study aimed to analyze historic changes in concentrations of trace elements in teeth of both species from 1941 to the present day. We analyzed the dentin of 94 canine teeth using stable isotope analysis (δ13C) and ICP-MS to determine their feeding areas and the concentration of 10 trace elements (Al, As, Cd, Cr, Cu, Fe, Mn, Ni, Pb, and Zn) respectively. The concentration of Cr was significantly higher during '70-'80s, in both species coinciding with tannery industry development. Both species of pinnipeds have been differentially exposed to trace elements depending on their feeding area. A pelagic diet, possibly based on squid, increased the concentration of Cd in A. australis, while O. byronia has been more exposed to anthropogenic Pb and Cu associated to a costal and more benthic diet. Our results highlight dentin as a reliable matrix for historic studies on the exposure to trace elements. In light of our results, the O. byronia's declining population could be the result of the synergistic effects of trace elements together with other ecological pressures faced in their environment.

Sedimentary record of hydrocarbons and sewage inputs from a highly populated region in South-Eastern Brazil.

The environmental impacts of the urban expansion in Rio de Janeiro was evaluated based on the historical accumulation of black carbon (BC), aliphatic (AHs) and aromatic hydrocarbons (PAHs) and sterols in a sediment core retrieved from Botafogo Cove. BC related to oil combustion sources increased significantly since the 1990s. AHs were associated with petroleum inputs and revealed a high level of contamination. Multivariate statistical methods (a Principal Component Analysis associated with a linear multiple regression - PCA/LMR) applied to PAHs suggests changes in the sources in recent years. This can be ascribed to a reduction in pyrogenic emissions over the last four decades and to an increase in petrogenic inputs since the 1990s. The sterol dinosterol registered the increased eutrophication over the last three decades, but the sewage marker coprostanol was present at relatively low concentrations (0.40 to 1.16 µg g-1) probably caused by enhanced bacterial activity in the sediment.

Air quality monitoring assessment during the 2016 Olympic Games in Rio de Janeiro, Brazil.

In 2009, the city of Rio de Janeiro was announced as the host city of the 2016 Olympic Games (Rio 2016). For this event, the Brazilian government, in partnership with the International Olympic Committee (IOC), undertook the task of monitoring the air quality in the city. This study discusses the PM10, PM2.5, and O3 profiles at ten sampling sites located near the arenas in 2016, including during the Olympic Games period. At all sampling stations, the annual mean values of PM10 and PM2.5 were below either Brazilian air quality standards or United States Environmental Protection Agency (U.S. EPA) guidelines. In addition, no violations lasting 24 h were observed for particulate matter in 2016. Only two ozone episodes occurred in 2016, both in Campos dos Afonsos (163 and 195 µg m-3) near the extreme sports arena. However, during the pre-Olympic period (2013-2015), in the same area were registered 16, 81, and 18 violations per year, respectively. The results showed an improvement in air quality in Rio de Janeiro in 2016. The reduction in pollutant levels, especially O3 and PM2.5, is probably due to the conclusion of the structural construction of the Olympic arenas and efforts to improve urban mobility.

Decadal and spatial variation of Hg concentrations in sediments of a multi-stressor impacted estuary.

The present study has evaluated temporal and spatial mercury trends based on surficial sediment samples and 210Pb-dated sediment profiles. The obtained results show that there are areas close to the main bay's tributary rivers where the Hg content has doubled during the last 15 years and regions where it has decreased by a factor of 2, mainly the area close to the navigation channel, which is submitted to periodic dredging. In the inner part of the bay, the most contaminated region, mercury shows a strong association with sulfide. In the same region, based on the 210Pb results, it was possible to calculate the yearly increment on the Hg concentration in the surface sediment, 0.62 µg kg-1 y-1 to 0.29 µg kg-1 y-1, according to the distance to the bay's main tributary rivers.

Inter-laboratory test for oxygen and hydrogen stable isotope analyses of geothermal fluids: Assessment of reservoir fluid compositions.

RATIONALE: Knowledge of the accuracy and precision for oxygen (δ18 O values) and hydrogen (δ2 H values) stable isotope analyses of geothermal fluid samples is important to understand geothermal reservoir processes, such as partial boiling-condensation and encroachment of cold and reinjected waters. The challenging aspects of the analytical techniques for this specific matrix include memory effects and higher scatter of delta values with increasing total dissolved solids (TDS) concentrations, deterioration of Pt-catalysts by dissolved/gaseous H2 S for hydrogen isotope equilibration measurements and isotope salt effects that offset isotope ratios determined by gas equilibration techniques. METHODS: An inter-laboratory comparison exercise for the determination of the δ18 O and δ2 H values of nine geothermal fluid samples was conducted among eleven laboratories from eight countries (CeMIEGeo2017). The delta values were measured by dual inlet isotope ratio mass spectrometry (DI-IRMS), continuous flow IRMS (CF-IRMS) and/or laser absorption spectroscopy (LAS). Moreover, five of these laboratories analyzed an additional sample set at least one month after the analysis period of the first set. Statistical evaluation of all the results was performed to obtain the expected isotope ratios of each sample, which were then subsequently used in deep reservoir fluid composition calculations. RESULTS: The overall analytical precisions of the measurements were ± 0.2‰ for δ18 O values and ± 2.0‰ for δ2 H values within the 95% confidence interval. CONCLUSIONS: The measured and calculated δ18 O and δ2 H values of water sampled at the weir box, separator and wellhead of geothermal wells suggest the existence of hydrogen and oxygen isotope-exchange equilibrium between the liquid and vapor phases at all sampling points in the well. Thus, both procedures for calculating the isotopic compositions of the deep geothermal reservoir fluid - using either the analytical data of the liquid phase at the weir box together with those of vapor at the separator or the analytical data of liquid and vapor phases at the separator -are equally valid.

Determination of (226)Ra in produced water by liquid scintillation counting.

It is proposed a method for the determination of (226)Ra in offshore platform liquid effluent samples (produced water). The method is based on a two-phase liquid scintillation counting system and allows for the direct and simple determination of (226)Ra content. Samples with high barium content may also have high (226)Ra concentration. Therefore, the sample volume is based on the barium concentration and ranges from 10 mL to 100 mL. Our new method was tested using multiple real samples and was compared with the BaSO4 precipitation method. The results based on the LSC were 30% higher than the precipitation method, which is attributed to the self-absorption of alpha particles in the BaSO4 precipitate. The determination of both (226)Ra and (228)Ra in the liquid effluent of offshore oil platforms is mandatory in Brazil. Thus, a second method of accurately assessing (228)Ra content remains necessary.

Investigation of thermostable metalloproteins in Perna perna mussels from differentially contaminated areas in Southeastern Brazil by bioanalytical techniques.

Metallomic studies regarding environmental contamination by metals are of value in elucidating metal uptake, trafficking, accumulation and metabolism in biological systems. Many proven bioindicator species, such as bivalves, have not yet, however, been well-characterized regarding their metalloprotein expression in response to environmental contaminants. In this context, the aim of the present study was to investigate metalloprotein expressions in the thermostable protein fraction of muscle tissue and digestive glands from mussels (Perna perna) from three differentially metal-contaminated sites in Southeastern Brazil in comparison with a reference site. The thermostable protein fractions were analyzed by SDS-PAGE and SEC-HPLC-ICP-MS. Metal content was also determined in both the crude and the purified extracts. Several inter-organ differences were observed, which is to be expected, while inter-site differences regarding thermostable protein content were also verified, indicating accumulation of these elements in muscle tissue and digestive glands and disruption of homeostasis of essential elements, with detoxification attempts by metal-bound proteins, since all metalloproteins present in both matrices eluted bound to at least one non-essential metal. These results are also noteworthy with regard to the adopted reference site, that also seems to be contaminated by toxic metals.

Vehicular Emission Ratios of VOCs in a Megacity Impacted by Extensive Ethanol Use: Results of Ambient Measurements in São Paulo, Brazil.

The São Paulo Metropolitan Area (SPMA) is a megacity with 20 million people and over 8 million vehicles. Over the past decade a large increase in biofuel usage, more notably ethanol by light-duty vehicles, has made Brazil, and in particular São Paulo, a unique case worldwide. This study presents the first assessment of emission ratios of a selected group of volatile organic compounds (VOCs) relative to carbon monoxide (CO) under ambient conditions. The VOCs studied here include aromatics such as benzene (1.03 pptv/ppbv CO), toluene (3.10 pptv/ppbv CO) and Oxygenated VOCs such as methanol (5.39 pptv/ppbv CO), acetaldehyde (3.93 pptv/ppbv CO), acetone (3.59 pptv/ppbv CO), methyl ethyl ketone (1.42 pptv/ppbv CO), and others. Despite the specificity of the fuel composition, emission ratios were in surprisingly close agreement with other megacities in Europe or in North America. Such results include species whose emission factors have been previously reported to decline (e.g., benzene) or increase (e.g., acetaldehyde) with ethanol usage. Furthermore, diurnal profiles and temperature analysis aid separating the primary anthropogenic, secondary or biogenic components of the species studied here. This study shows that a significant fraction of ethanol in gasoline blends does not result in a well-defined trend in VOC emission profile and certainly motivates further studies.

Assessment of trace elements, POPs, (210)Po and stable isotopes ((15)N and (13)C) in a rare filter-feeding shark: The megamouth.

With less than 60 records being reported worldwide, the megamouth (Megachasma pelagios) is today one of the least known shark species inhabiting our oceans. Therefore, information concerning the biology and ecology of this enigmatic organism is very scarce and limited to feeding behaviour and preferred habitat. The present work reports new data on the concentrations of trace elements, organic mercury, POPs and (210)Po in hepatic and muscular tissues of a specimen found stranded in the southeastern coast of Brazil. Additionally, we provide new evidence based on stable isotope analysis (δ(15)N and δ(13)C) confirming the preference for the pelagic habitat and the zooplanktivorous feeding behaviour of the megamouth. These results are consistent with the low concentrations of organic pollutant compounds and other elements measured in our samples.

Tritium ((3)H) as a tracer for monitoring the dispersion of conservative radionuclides discharged by the Angra dos Reis nuclear power plants in the Piraquara de Fora Bay, Brazil.

Presently, two nuclear power plants operate in Brazil. Both are located at Itaorna beach, Angra dos Reis, approximately 133 km from Rio de Janeiro city. The reactor cooling circuits require the input of seawater, which is later discharged through a pipeline into the adjacent Piraquara de Fora Cove. The radioactive effluents undergo ion-exchange treatment prior to their release in batches, causing the enrichment of (3)H relative to other radionuclides in the discharged waters. Under steady state conditions, the (3)H gradient in the Piraquara de Fora waters can be used to determine the dependence of the dilution factor on the distance from the discharge point. The present work describes experiments carried out at the reactor site during batch release episodes, including time series sampling at the discharge point and surface seawater sampling every 250 m to a distance of 1250 m, after a double distillation, the (3)H concentration was measured by liquid scintillation counting applying a Quantulus liquid scintillation spectrometer. The obtained results showed a linear relationship between the (3)H concentration and distance from the discharge point. At 1250 m from the discharge point a dilution index of 1:15 was measured which fits the expected value based on modeling.

(210)Polonium and (210)lead content of marine birds from Southeastern Brazil.

In this study, we report the (210)Po and (210)Pb concentrations of bone, muscle and liver samples that were obtained from twelve different marine bird species stranded on beaches in the central-north region of Rio de Janeiro State. Both radionuclides were highly concentrated in the liver samples; however, the lowest mean (210)Po/(210)Pb activity ratio (1.3) was observed in bones compared with liver and muscle (16.8 and 13.8, respectively). Among the species that were studied, Fregata magnificens, with a diet based exclusively on fish, had the lowest (210)Pb and (210)Po concentrations and the lowest (210)Po/(210)Pb activity ratio. The (210)Po concentrations in Puffinus spp. liver samples followed a log-normal distribution, with a geometric mean of 300 Bq kg(-1)wet weight. Only two references pertaining to (210)Po in marine birds were found in a Web of Science search of the literature, and each study reported a different concentration value. The values determined in this experiment are consistent with those in one of the previous studies, which also included one of the species studied in this work. No values for (210)Pb in marine birds have been published previously.

210Polonium content of small cetaceans from Southeastern Brazil.

The (210)Po concentration of muscle and liver samples obtained from dolphins stranded on beaches in the Southeastern region of Rio de Janeiro State was analyzed in the present study. The samples were primarily obtained from "Franciscana" (Pontoporia blainvillei) and "Guiana" dolphins (Sotalia guianensis); however, samples from four other species were also evaluated. The (210)Po concentration of muscle samples obtained from "Franciscana" dolphins (66.7±6.7, n=8)Bq kg(-1)w.w. was greater than that of "Guiana" dolphins (25.3±5.7, n=8)Bq kg(-1)w.w. due to differences in the diets of these species. Alternatively, the (210)Po concentrations of liver samples obtained from different species were statically equivalent. Compared to the results described in the literature, the muscle samples evaluated in the present study displayed lower (210)Po concentrations, except for those obtained from "Franciscana" dolphins, which exhibited similar values. For "Franciscana" and "Guiana" dolphins, a clear relationship between the (210)Po concentration of muscle and liver samples and the size of the dolphin was not observed.

Geochronology of anthropogenic radionuclides in Ribeira Bay sediments, Rio de Janeiro, Brazil.

Ribeira Bay is located approximately 130 km south of the city of Rio de Janeiro and receives discharges of liquid effluent from the Angra dos Reis nuclear power plant (NPP) site, where two pressurized water reactors are located. To test whether the presence of anthropogenic radionuclides in sediments in Ribeira Bay could be correlated to the NPP operations, we sampled seven sediment cores and determined accumulation rates and chronologies. Only one sediment core did not exhibit a superficial mixing layer; this sample was used for dating purposes. Cesium-137 and (207)Bi were observed in this sediment profile, but their presence was associated with atmospheric fall-out rather than the nearby NPP. The exponential decay of (210)Pb concentration with sediment layer depth was verified below a superficial mixing layer for all other sediment cores. Calculated accumulation rates ranged from 1.2 mm y(-1) in the inner bay to 6.2 mm y(-1) close to its entrance.

Use of multitracers for the study of water mixing in the Paraíba do Sul River estuary.

Multitracers were used to study water mixing in the Paraíba do Sul River estuary region in August 2007 (dry season) and March 2008 (rainy season) and to evaluate the reach of the river plume in the direction of the open ocean. Two sampling campaigns were carried out, each in a different season. Based on these results, it was possible to conclude that the multitracers used in this study (salinity, Si, Ba and U, as well as the radium isotopes 223Ra, 224Ra, 226Ra and 228Ra) presented satisfactory results toward defining the plume reach and determining the residence time and water-mixing processes in the estuary. A strong correlation was observed between tracers and the distance to the coast. During the low river water discharge period, the riverine water took about 10 days to reach open ocean waters (salinity approximately 35). During the rainy period this value decreased to 6 days. Based on the radium results, it was possible to calculate diffusion coefficients (K(h)) of 23 km(2) d(-1) and 38 km(2) d(-1) for 224Ra and 223Ra, respectively, during the dry season (winter). Values of 65 km(2) d(-1) and 68 km(2) d(-1) for 223Ra and 224Ra, respectively, were found for the rainy period (summer).

Determination of total content and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes by ICP-QMS.

The aim of this work was to determine the concentrations and isotopic compositions of plutonium and uranium in environmental samples for safeguards purposes. An analytical method was developed with a plutonium and uranium separation procedure based on extraction chromatography (using 2mL TEVA and UTEVA columns) and detection with a quadrupole ICP-MS applying an ultra-sonic nebulizer coupled with a membrane desolvation system. Starting from blank swipes, the background equivalent concentration (BEC) was 8fg for (239)Pu and 1ng (238)U. The method was successfully applied to certified reference materials as well as to round robin samples obtained in the framework of the inter-laboratory exercise program, promoted by the Brazilian-Argentine Agency for Accounting and Control of Nuclear Materials (ABACC), together with the US Department of Energy (USDOE). After the introduction of an additional ion-exchange separation step, the methodology was applied to the IAEA-384 sediment reference sample with precise and accurate total plutonium and uranium, (240)Pu/(239)Pu, (241)Pu/(239)Pu, (234)U/(238)U and (235)U/(238)U atomic ratio results.

Metal concentrations, fluxes, inventories and chronologies in sediments from Sepetiba and Ribeira Bays: a comparative study.

Three sediment cores were sampled at Sepetiba Bay and four cores at Ribeira Bay, Rio de Janeiro State, Brazil. Sediment accumulation rates and chronologies were obtained from (210)Pb activity-depth profiles. Sediment accumulation rates in Ribera Bay ranged from 1.2 mm y(-1) in the inner bay to 2.6 mm y(-1) close to its entrance. In Sepetiba Bay two sediment accumulation rates were observed: a lower rate of 0.35 cm y(-1) before the 1960s and 0.76 cm y(-1) since then. The cause of this change is due to the construction of the Santa Cecília impoundment (1955) that brings water from the Paraíba do Sul Basin into the Guandu River, which increased its flow from the original 20 m(3)s(-1) to 160 m(3)s(-1). Concentration of 44 elements was obtained by ICP-MS after total dissolution of samples from two selected cores. The relative differences between the concentrations of crustal elements, such as Al, Fe and Ti are only about 20% (p<0.05). Cd and Zn are 15 and four times larger in Sepetiba Bay than in Ribeira Bay, respectively. Other major and minor elements show lower statistically significant differences. The enrichment factors and metal inventories show that Sepetiba Bay can be considered polluted with Bi, Cd, Cr, Cu, Sb and Zn. Particularly, Cd and Zn present concentrations three and four times higher than the Brazilian existing limits.