Metal record of copper-based antifouling paints in sediment core following marina construction and operation.

Marinas are central hubs of global maritime leisure and transport, yet their operations can deteriorate the environmental quality of sediments. In response, this study investigated the metal contamination history associated with antifouling paint uses in a sediment core collected from Bracuhy marina (Southeast Brazil). Analysis target major and trace elements (Cu, Zn, Pb, Cd and Sn), rare earth elements (REEs), and Pb isotopes. The modification in Pb isotopic ratios and REEs pattern unequivocally revealed sediment provenance disruption following the marina construction. Metal distribution in the sediment core demonstrates that concentrations of Cu and Zn increased by up to 15 and 5 times, respectively, compared to the local background. This severe Cu and Zn contamination coincides with the onset of marina operations and can be attributed to the use of antifouling paints.

Adapted Sequential Extraction Protocol to Study Mercury Speciation in Gold Mining Tailings: Implications for Environmental Contamination in the Amazon.

Artisanal small-scale gold mining (ASGM), an increasingly prevalent activity in South America, generates mercury-contaminated tailings that are often disposed of in the environment, leading to the introduction of mercury into ecosystems and the food web, where it bioaccumulates. Therefore, studying the geochemical processes involved in the desorption and dissolution of mercury in these tailings is essential for critical risk evaluations in the short and long term. For this purpose, sequential extraction procedures (SEPs) can be useful because they help to identify the phases to which Hg is associated, although they also have limitations such as a lack of selectivity and specificity. In this work, we propose a modified four-step SEP: exchangeable mercury (F1), oxidizable mercury (F2), mercury bound to Fe oxides (F3), and strongly bound mercury (F4). To test this adapted sequential extraction method, we evaluated the Hg contamination in mercury-contaminated tailings of the Amazon basin. The results revealed a total mercury concentration of 103 ± 16 mg·kg-1 in the tailings, with a significant portion in F1 (28% of the total), where Hg was bioavailable. The large Hg concentration in F3 (36%) suggested that Fe oxides likely contribute to mercury retention. Together, the SEP results emphasize the urgent need for improved surveillance of gold mining activities and responsible tailings management practices to mitigate environmental contamination and safeguard the health of the Amazon ecosystem.

Exploring a new approach for assessing the fate and behavior of the tailings released by the Brumadinho dam collapse (Minas Gerais, Brazil).

In 2019, the Brumadinho dam rupture released a massive amount of iron ore mining tailings into the Paraopeba River. Up to now, it remains a public health issue for the local and downstream populations. The present study aims to assess the behavior and fate of metal contamination following the disaster. Using new sampling strategies and up-to-date geochemistry tools, we show that the dissolved metal concentrations (< 0.22 µm cutoff filtration) remained low in the Paraopeba River. Although the tailings present high metal concentrations (Fe, Mn, Cd, and As), the high local background contents of metals and other previous anthropogenic contamination hamper tracing the sediment source based only on the geochemical signature. The Pb isotopic composition coupled with the metals enrichment factor of sediments and Suspended Particulate Matter (SPM) constitutes accurate proxies that trace the fate and dispersion of tailing particles downstream of the dam collapse. This approach shows that 1) The influence of the released tailing was restricted to the Paraopeba River and the Retiro Baixo reservoir, located upstream of the São Francisco River; 2) The tailings' contribution to particulate load ranged from 17 % to 88 % in the Paraopeba River; 3) Other regional anthropogenic activities also contribute to water and sediment contamination of the Paraopeba river.

New insights into metal(loid) dynamics in the Doce River estuary (Brazil) after a massive iron ore-processing tailing dam collapse.

The present study investigated metal and metalloid dynamics in the estuarine water of the Doce River (Brazil) after the collapse of an iron ore-processing tailing dam in 2015. Spectroscopic and isotopic techniques were applied to bring new insights into the effects of the dam failure on the dynamics and hazardousness of particulate and dissolved metal(loid) concentrations along the fluvial-estuarine continuum. Spectroscopic analysis showed that the suspended particulate matter (SPM) of the Doce River estuary consisted of a combination of soil-delivered particles and fine tailing mud particles with small amounts of coarse tailing mud Fe oxides (~150-µm width). Enrichment and contamination factors showed that the dam failure increased particulate Fe, Pb, Cd, and As, and dissolved Pb concentrations. Total concentrations of As (15 µg/L), Pb (30 µg/L), Cd (8 µg/L), and Cr (105 µg/L) increased up to values higher than quality and regulatory guidelines. Human health risk assessment showed that local communities are exposed to a potentially chronic Cr noncarcinogenic effects, although Cr high concentrations were not linked with the dam failure by this study. The particulate Pb isotope signatures reported herein (206/207Pb ratios of 1.214 ± 0.006 and 208/206Pb ratios of 2.025 ± 0.011) can be applied to constrain metal(loid) sources in the Doce River sediment plume and continental shelf. The river-ocean mixing zone caused abrupt changes metal(loid) partitioning (Zn, Pb, Cr, Cu, Cd, and As), controlling their fate in the estuary and the Brazilian southeast coastal.

Trace metal dynamics in an industrialized Brazilian river: A combined application of Zn isotopes, geochemical partitioning, and multivariate statistics.

The Paraiba do Sul (PSR) and Guandu Rivers (GR) water diversion system (120 km long) is located in the main industrial pole of Brazil and supplies drinking water for 9.4 million people in the metropolitan region of Rio de Janeiro. This study aims to discern the trace metals dynamics in this complex aquatic system. We used a combined approach of geochemical tools such as geochemical partitioning, Zn isotopes signatures, and multivariate statistics. Zinc and Pb concentrations in Suspended Particulate Matter (SPM) and sediments were considerably higher in some sites. The sediment partition of As, Cr, and Cu revealed the residual fraction (F4) as the main fraction for these elements, indicating low mobility. Zinc and Pb were mostly associated with the exchangeable/carbonate (F1) and the reducible (F2) fractions, respectively, implying a higher susceptibility of these elements to being released from sediments. Zinc isotopic compositions of sediments and SPM fell in a binary mixing source process between lithogenic (δ66/64ZnJMC ≈ + 0.30‰) and anthropogenic (δ66/64ZnJMC ≈ + 0.15‰) end members. The lighter δ66/64ZnJMC values accompanied by high Zn concentrations in exchangeable/carbonate fraction (ZnF1) enable the tracking of Zn anthropogenic sources in the studied rivers. Overall, the results indicated that Hg, Pb, and Zn had a dominant anthropogenic origin linked to the industrial activities, while As, Cr, and Cu were mainly associated with lithogenic sources. This work demonstrates how integrating geochemical tools is valuable for assessing geochemical processes and mixing source effects in anthropized river watersheds.

Behavior of metallurgical zinc contamination in coastal environments: A survey of Zn from electroplating wastes and partitioning in sediments.

The contamination of coastal environments by metallurgical wastes involves multiple biogeochemical processes; accordingly, understanding metal behavior and risk evaluation of contaminated areas, such as Sepetiba Bay (Rio de Janeiro, Brazil), remains challenging. This study coupled Zn isotopic analyses with sequential extractions (BCR) to investigate the mechanisms of Zn transfer between legacy electroplating waste and the main environments in Sepetiba Bay. This metallurgical waste showed a light bulk isotopic signature (δ66/64ZnbulkJMC = +0.30 ±â€¯0.01‰, 2 s, n = 3) that was not distinct from the lithogenic geochemical baseline, but was different from signature of mangrove sediment considered as anthropogenic end member (δ66/64ZnJMC = +0.86 ±â€¯0.15‰) in a previous isotopic study in this area. Zn isotopic compositions of sediment samples (ranging from +0.20 to +0.98‰) throughout the bay fit a mixing model involving multiple sources, consistent with previous studies. In the metallurgic zone, the exchangeable/carbonate fraction (ZnF1) exhibited high Zn concentrations (ZnF1 = 9840 µg g-1) and a heavy isotopic composition (δ66/64ZnF1JMC = +1.10 ±â€¯0.01‰). This finding showed that, in some cases, the bulk isotopic signature of waste is not the most relevant criterion for evaluating trace metal dispersion in the environment. Indeed, based on the BCR, it was observed that part of the anthropogenic metallurgical Zn was redistributed from the exchangeable/carbonate fraction in the waste to the surrounding mangrove sediment. Then, this contaminated sediment with heavy δ66/64Zn values was exported to other coastal environments. In Sepetiba Bay, contaminated sediments revealed a large concentration of ZnF1 fraction (up to 400 µg g-1) with a heavy Zn isotopic signature. This signature also matched the Zn isotopic signature of oysters in Sepetiba Bay reported by other studies; hence, measurement of the isotopic exchangeable/carbonate fraction has important implications for tracing the transfer of anthropogenic Zn to biota.

Rapid neodymium release to marine waters from lithogenic sediments in the Amazon estuary.

Rare earth element (REE) concentrations and neodymium isotopic composition (ɛNd) are tracers for ocean circulation and biogeochemistry. Although models suggest that REE release from lithogenic sediment in river discharge may dominate all other REE inputs to the oceans, the occurrence, mechanisms and magnitude of such a source are still debated. Here we present the first simultaneous observations of dissolved (<0.45 µm), colloidal and particulate REE and ɛNd in the Amazon estuary. A sharp drop in dissolved REE in the low-salinity zone is driven by coagulation of colloidal matter. At mid-salinities, total dissolved REE levels slightly increase, while ɛNd values are shifted from the dissolved Nd river endmember (-8.9) to values typical of river suspended matter (-10.6). Combining a Nd isotope mass balance with apparent radium isotope ages of estuarine waters suggests a rapid (3 weeks) and globally significant Nd release by dissolution of lithogenic suspended sediments.

Hidroquímica do rio Solimões na região entre Manacapuru e Alvarães: Amazonas - Brasil

The present study evaluated the physical and chemical characteristics of the water of the rivers Solimões, Purus and their tributaries, collected in November of 2004 in the State of Amazonas between the cities of Manacapuru and Alvarães and Anamã and Pirarauara. Physical-chemical analyses (temperature, pH, electrical conductivity, turbidity, Ca2+, Na+, K+, Mg2+, HCO3-, SO4(2-), Cl-), and trace-elements (Li, B, Al, Sc, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Rb, Sr, Mo, Cd, Sb, Cs, Ba, Pb, La, Ce e U) and Sr isotopes were accomplished. The analyzed parameters and the chemical composition show that the waters of the rivers and tributaries of the central region of the Amazonia are chemically distinct between them. The white waters of Solimões are calcium-bicarbonate and of Purus are bicarbonates, and the respectives tributaries are sodium-potassium-bicarbonate and sodium-potassium-sulphate. This causes the white poorly acided waters to the neutrals and more conductives, while the black ones are less mineralized, more acids, mainly of Purus. The Ba, Sr, Cu, V e As in highest levels differentiate the Solimões white waters of the Purus`s waters, well as the tributaries of the first related to the second. This complex of caracteristics indicates that the Solimões as the Purus and their respectives tributaries are submitted to geological/ambiental distinct conditions. The influence of arrives in port of sediments of Andes is diluted at the currency of basin of the Solimões and it reflects on formation of fertile valleys Solimões and Purus. By another view, the crust rocks, represented by the Shields of the Guianas and Brasileiro both contribute, but in a reduced proportion.

Este trabalho discute as características físico-químicas das águas dos rios Solimões, Purus e seus afluentes, coletadas em novembro de 2004 no Estado do Amazonas, entre as cidades de Manacapuru-Alvarães e Anamã-Pirarauara. Foram realizadas análises físico-químicas (temperatura, pH, condutividade elétrica, turbidez, Ca2+, Na+, K+, Mg2+, HCO3-, SO4(2-), Cl-), de elementos-traço (Li, B, Al, Sc, V, Cr, Mn, Fe, Co, Cu, Zn, As, Se, Rb, Sr, Mo, Cd, Sb, Cs, Ba, Pb, La, Ce e U) e isótopos de estrôncio. Os parâmetros analisados e a composição química mostram que as águas dos rios e igarapés da região central da Amazônia são quimicamente distintas entre si. As águas brancas do Solimões são cálcicas-bicarbonatadas e as do Purus bicarbonatadas, os respectivos afluentes são sódico-potássico-bicarbonatados e sódico-potássico-sulfatados. Isso acarreta águas brancas fracamente ácidas a neutras e mais condutivas, enquanto as pretas são menos mineralizadas, mais ácidas, especialmente as do Purus. O Ba, Sr, Cu, V e As mais elevados diferenciam as águas brancas do Solimões das do Purus, bem como os afluentes do primeiro em relação ao segundo. Esse conjunto de características indicam que tanto o Solimões, como o Purus e os respectivos afluentes, estão submetidos a condições geológicas/ambientais distintas. A influência do aporte de sedimentos dos Andes é diluída ao longo da bacia do Solimões e se reflete na formação das várzeas dos Solimões e Purus. Por outro lado as rochas crustais, representadas pelos escudos das Guianas e Brasileiro também contribuem, mas em menor proporção.

The influence of the Amazonian floodplain ecosystems on the trace element dynamics of the Amazon River mainstem (Brazil).

The purpose of this paper is to forecast the role of riverine wetlands in the transfer of trace elements. One of the largest riverine wetlands in the world is the floodplain (várzea) of the Amazon River and its tributaries (Junk and Piedade, 1997). The central Amazon wetlands are constituted by a complex network of lakes and floodplains, named várzeas, that extend over more than 300,000 km2 (Junk, W.J., The Amazon floodplain--a sink or source for organic carbon? In Transport of Carbon and Minerals in Major World Rivers, edited by E.T. Degens, S. Kempe, R. Herrera, SCOPE/UNEP; 267-283, 1985.) and are among the most productive ecosystems in the world due to the regular enrichment in nutrients by river waters In order to understand if the adjacent floodplain of Amazon River have a significant influence on the trace element concentrations and fluxes of the mainstem, the concentrations of selected elements (i.e., Al, Mn, Fe, Co, Cu, Mo, Rb, Sr, Ba, and U) have been measured in the Amazon River water (Manacapuru Station, Amazonas State, Brazil) and in lake waters and plants (leaves) from a várzea(Ilha de Marchantaria, Amazonas State, Brazil) during different periods of the hydrological cycle. Four plant species (two perennial species: Pseudobombax munguba and Salix humboldtiana, and two annual herbaceous plants: Echinochloa polystachya and Eichhornia crassipes) were selected to represent the ecological functioning of the site. Time series obtained for dissolved Mn and Cu (<0.20 microm) in Amazon River water could not be explained by tributary mixing or instream processes only. Therefore, the contribution of the waters transiting the floodplains should be considered. These results suggest that the chemical composition of the waters draining these floodplains is controlled by reactions occurring at sediment-water and plant-water interfaces. Trace elements concentrations in the plants (leaves) vary strongly with hydrological seasonality. Based on the concentration data and the biological productivity of floodplain ecosystems, a first order approximation of trace element storage (permanent or temporary) in the vegetation of these floodplains was made. It was found that floodplain-mainstem elemental fluxes make a significant contribution to the dissolved flux of the Amazon River. This study is part of the Brazilian_French joint research program Hybam (Hydrology and Geochemistry of the Amazonian Basin).