Assessing heavy metal contamination in a Brazilian metropolis: a case study with a focus on (bio)indicators.

The continuous expansion of the global vehicle fleet poses a growing threat to environmental quality through heavy metal contamination. In this scenario, monitoring to safeguard public health in urban areas is necessary. Our study involved the collection of 36 street dust and 29 moss samples from roads of a Brazilian metropolis (Recife) with varying traffic intensities as follows: natural reserve (0 vehicles per day), low (< 15,000 vehicles per day), medium (15,000-30,000 vehicles per day), and high (> 30,000 vehicles per day). ICP-AES analysis was performed to determine the concentrations of nine potentially toxic metals (Ba, Cd, Cr, Cu, Mn, Ni, Pb, V, and Zn) to assess the influence of vehicular flow on urban contamination. In the street dust samples, the mean metal concentrations (mg kg-1) exhibited the following order: Ba (503.7) > Mn (303.0) > Zn (144.4) > Cu (95.3) > Cr (56.1) > Pb (34.2) > V (28.7) > Ni (11.3) > Cd (1.5). Conversely, in the moss samples, the metal concentration order was as follows (mg kg-1): Mn (63.8) > Zn (62.5) > Ba (61.0) > Cu (17.7) > Cr (8.0) > V (7.3) > Pb (7.0) > Ni (2.9) > Cd (0.3). Roads with higher traffic volumes exhibited the highest metal enrichments in moss samples for all metals and in dust samples for Cd, Cr, Mn, Ni, and V. However, dust from low-flow roads had higher enrichments for Ba, Cu, and Zn, indicating the influential role of other traffic-related factors in metal deposition. Our findings highlight traffic flow as the predominant source of pollution in urban centers, with both street dust and moss serving as sensitive indicators of metal input attributable to vehicular traffic. These indicators offer valuable insights for urban quality monitoring and pollution control efforts.

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

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

Baseline concentrations, source apportionment, and probabilistic risk assessment of heavy metals in urban street dust in Northeast Brazil.

Heavy metal pollution by accelerating urbanization is an emerging socio-environmental issue that poses a potential risk to human health and the environment. In this scenario, street dust is a primary source of contaminants. Here, the metal concentrations in street dust of one of the biggest Brazilian cities were assessed aiming to identify and quantify the sources of contamination. The metal bioaccessibility and estimated probabilistic (non)-carcinogenic risks to humans were also evaluated. Thirty-six dust samples were collected in the metropolitan region of Recife. Results showed that the traffic governed the distribution and accumulation of metals in street dust. Emissions from vehicles were the primary source (> 70 %) of heavy metals, except for Cd, which had a mixed origin (natural, traffic, and industrial). Moderate to heavy dust contamination by Ba, Cu, Mn, Pb, and Zn were found, with a very high potential ecological risk. The main exposure route depended on the metal. Barium, Cu, and Pb had ingestion rather than dermal contact as the main route of exposure, while inhalation and dermal contact posed the main risks to Mn and Cr, respectively. The risk for children was higher than for adults. The probabilities of unacceptable carcinogenic risk scenarios (TCRI >10-6) for children and adults were 27 and 4 %, respectively, with Cr being the most concerning metal for the health of the urban population.

Geospatial modeling and ecological and human health risk assessments of heavy metals in contaminated mangrove soils.

Heavy metal-contaminated wastes can threaten mangrove forests, one of the most biodiverse ecosystems in the world. The study evaluated the geospatial distribution of heavy metals concentrations in soils, the ecological and human health risks, and metal contents in soil fractions and mangrove organisms in the Botafogo estuary, Brazil, one of the most environmentally impacted estuaries in the country. The metal concentrations exceeded by up to 2.6-fold the geochemical background; 91%, 59%, 64%, 31%, and 82% of the soils were contaminated with Cr, Zn, Pb, Cu, and Ni, respectively. Adverse effects to the biota may occur due to Cr, Cu, Ni and Pb exposures. Contents of clay and organic matter were the main factors governing the distribution of metals in soil, contributing to up to 63% of the total variability. However, the geospatial modeling showed that the predictive ability of these variables varied spatially with the metal and location. The ecological and human health risks assessments indicated that the metal concentrations in soils are safe for the environment and human beings. There was a low transfer of metals from the soil to the biota, with values of sediment-biota accumulation factor (SBAF) and biological accumulation coefficients (BAC) lower than 1.0, except for Zn (SBAF = 13.1). The high Zn bioaccumulation by Crassostrea rhizophorae may be associated with the concentrations of Zn in the bioavailable fractions.

Assessing the spatial distribution and ecologic and human health risks in mangrove soils polluted by Hg in northeastern Brazil.

The emission of mercury (Hg) by chlor-alkali plants can pollute soils and sediments, posing risks to the environment and human health. Mangrove ecosystems are particularly sensitive to Hg contamination. Here, we studied the Hg spatial distribution and associated human and ecologic risks in mangrove soils impacted by a chlor-alkali plant. Sixty-six samples of superficial soils were collected from the mangrove of the Botafogo River, Brazil. Mercury contents were determined and ecological and human health risks were estimated from the soil. The Hg contents exceeded the local Hg background by up to 180 times, indicating the substantial anthropic contribution that occurred in the area. Mercury concentrations followed a gradient as a function of the distance from the chlor-alkali plant, with an apparent contribution from the estuary's hydrodynamic regime. The ecological risk was considered high in all the soils evaluated, while the daily average exposure for humans, considering multiple exposure routes to soil, is below the tolerable dose recommended by the World Health Organization (WHO). However, the risk to human health was unacceptable in the estuary section closest to the plant, mainly for children. Vapor inhalation was the main route for estimating non-carcinogenic risk. The results of this study indicate a severe scenario of Hg pollution with unacceptable risks to the ecosystem and the health of human beings, especially of the communities that live from fishery and shellfish colletion and are exposed daily to soils polluted by mercury. Studies on the organomercurial species in the food chain and Hg levels in individuals living close to the estuary are warranted. This research is an important reference in the world regarding the contamination of mangrove areas by Hg.

Bioavailability and sequential extraction of mercury in soils and organisms of a mangrove contaminated by a chlor-alkali plant.

Botafogo river estuary poses the highest Hg concentration reported for mangrove soils in Brazil. Such high contamination took place owing to the improper waste disposal for 24 years from a chlor-alkali plant nearby the estuary. Here we determined Hg concentrations in soils, mangrove plants (Rhizophora mangle and Laguncularia racemosa), and an aquatic organism (the oyster species Crassostrea rhizophorae) to assess Hg bioavailability. Besides, a sequential extraction procedure was used to separate soil Hg into five fractions: water-soluble; 'human stomach acid' soluble; organically bound; elemental Hg; mercuric sulfide. Results showed that environmentally available concentration of Hg in the mangrove soils were up to 150-fold higher than a pristine mangrove under the same geological context used as a reference. Additionally, Hg concentration in soils was also above sediment quality guidelines and Hg adverse effects towards sensitive estuarine organisms are likely. Mercury concentrations in oysters were the highest reported in Brazil, but within safety standards according to the country food security agency. It seems that Hg stocks in the studied soils are governed by organic matter and redox conditions, but changing on environmental conditions and land use can alter this balance and convert these mangrove areas from sink to source of Hg to the environment.

Assessing human health risks and strategies for phytoremediation in soils contaminated with As, Cd, Pb, and Zn by slag disposal.

Soils impacted by metallurgy activities pose serious risks to the health of exposed populations, whether by ingestion of soil or contaminated food and water. The municipality of Santo Amaro, Bahia state, presents the most important case of human lead contamination in Brazil. It occurred because of inadequate slag disposal. The aims of this research were to: (i) determine the environmentally available concentrations and the distribution of As, Cd, Pb, and Zn in soil fractions; (ii) estimate the non-carcinogenic and carcinogenic risks of these elements for children; and (iii) to evaluate the use of corn (Zea mays) and castor bean (Ricinus communis) either for phytoextraction induced by chelating agents or phytostabilization. Our data demonstrated that the environmentally available concentrations of As, Cd, Pb, and Zn in soils surrounding the Pb smelting plant are among the highest that have been reported. Apart from Cd, sequential extraction demonstrated that most metals are in recalcitrant forms in the soil. However, the daily exposure of children to Pb, Zn, Cd, and As exceeded the acceptable daily intake as established by the World Health Organization. Non-carcinogenic risk modeling indicated probable adverse health effects from chronic exposure to soil Pb. The mean estimated time for remediation of the area using phytoextraction was high, ranging from 76 to 259 years; therefore, this is not a viable alternative for remediating soils in the studied area. However, good development in the contaminated soil along with restriction of the metal(oid) translocation to shoots enables castor bean to phytostabilize metal(oid)s. Additionally, castor bean cultivation may be an alternative for an economic return because of biofuel production.

Assessing heavy metal sources in sugarcane Brazilian soils: an approach using multivariate analysis.

Brazil is the world's largest sugarcane producer and soils in the northeastern part of the country have been cultivated with the crop for over 450 years. However, so far, there has been no study on the status of heavy metal accumulation in these long-history cultivated soils. To fill the gap, we collect soil samples from 60 sugarcane fields in order to determine the contents of Cd, Cr, Cu, Ni, Pb, and Zn. We used multivariate analysis to distinguish between natural and anthropogenic sources of these metals in soils. Analytical determinations were performed in ICP-OES after microwave acid solution digestion. Mean concentrations of Cd, Cr, Cu, Ni, Pb, and Zn were 1.9, 18.8, 6.4, 4.9, 11.2, and 16.2 mg kg(-1), respectively. The principal component one was associated with lithogenic origin and comprised the metals Cr, Cu, Ni, and Zn. Cluster analysis confirmed that 68 % of the evaluated sites have soil heavy metal concentrations close to the natural background. The Cd concentration (principal component two) was clearly associated with anthropogenic sources with P fertilization being the most likely source of Cd to soils. On the other hand, the third component (Pb concentration) indicates a mixed origin for this metal (natural and anthropogenic); hence, Pb concentrations are probably related not only to the soil parent material but also to industrial emissions and urbanization in the vicinity of the agricultural areas.