Trophic position, altitudinal distribution, and water dependence as determining factors for mercury concentrations in tropical montane anurans.

Mercury (Hg) is a widespread and toxic contaminant with potential for long-range atmospheric transport. Previous work has shown that temperate and subtropical montane ecosystems have great potential for deposition of this element. However, little information exists regarding Hg dynamics in tropical mountains. In present study, we evaluated the influence of altitudinal distribution, size, trophic position, and degree of water dependence on Hg concentration in amphibians. For this purpose, we determined the mercury concentration in topsoil and amphibian samples collected at 32 points distributed between 327 and 2181 m above sea level in Serra dos Órgãos, a mountainous complex located in southeastern Brazil. We analyzed the concentration of mercury in whole body samples of 200 individuals of 30 amphibian species. Trophic position of the specimens was estimated by nitrogen stable isotope (δ15N) composition in muscle tissues. We observed a positive relationship between elevation and Hg concentration in topsoil samples from rainforest sites. However, in samples from nebular forest and campos de altitude (highland grasslands) sites, the concentration of Hg was considered lower than expected by the trend in rainforest points, indicating that the vegetation structure plays an important role in the deposition of atmospheric mercury. Mercury concentration in amphibians varies according to the functional characteristics of the species and the environment in which the individual is inserted. Elevation, trophic level and water dependence explained at least some degree of variation in Hg concentration in amphibian tissues. Thus, this community-level analysis suggests that mountainous areas in the tropical region, as recorded for temperate and subtropical mountains, act as regional convergence and deposition sites for atmospheric mercury.

Occurrence of pyrethroids in the atmosphere of urban areas of Southeastern Brazil: Inhalation exposure and health risk assessment.

The occurrence of organochlorine pesticides (OCPs) used decades ago for vector control in urban areas is still reported as a threat to human health. Pyrethroids emerged as a replacement for OCPs in sanitary campaigns and are currently the main insecticides used for vector control worldwide, with prominent use as agricultural and household insecticides, for veterinary and gardening purposes, and as wood preservative. This study aimed to assess the occurrence, seasonal variation, and potential sources of pyrethroids in ambient air of two urban regions of Southeastern Brazil, along with the potential health risks to local populations via inhalation exposure. Pyrethroids were sampled by polyurethane foam passive air samplers and their concentrations were determined by gas chromatography coupled with electron capture negative ionization mass spectrometry (GC/ECNI-MS). Atmospheric pyrethroid concentrations (hereinafter reported in pg m-3) were considerably higher than those reported by previous studies worldwide. Cypermethrin (median: 2446; range: 461-15 125) and permethrin (655; 19-10 328) accounted for 95% of the total measured pyrethroids in ambient air. The remaining fraction comprised smaller amounts of bifenthrin (46;  urban-industrial > background areas. HQs increased with decreasing age group, but deterministic and probabilistic estimates did not identify direct health risks for any group. Nevertheless, since only inhalation exposure was considered in this work, other pathways should be investigated to provide a more comprehensive risk assessment of the human exposure to pyrethroids.

Atmospheric Occurrence of Organochlorine Pesticides and Inhalation Cancer Risk in Urban Areas at Southeast Brazil.

Organochlorine pesticides (OCPs) have been produced for almost a century and some of them are still used, even after they have been proved to be toxic, persistent, bioaccumulative and prone to long-range transport. Brazil has used and produced pesticides in industrial scales for both agricultural and public health purposes. Urban and industrial regions are of special concern due to their high population density and their increased exposure to chemical pollution, many times enhanced by chemical production, application or irregular dumping. Therefore, we aimed to investigate the occurrence of OCPs in outdoor air of urban sites from two major regions of southeast Brazil. Some of these sites have been affected by OCP production and their irregular dumping. Deterministic and probabilistic inhalation cancer risk (CR) assessments were conducted for the human populations exposed to OCPs in ambient air. Ambient air was mainly affected by Æ©-HCH (median = 340 pg m-3) and Æ©-DDT (median = 233 pg m-3), the only two OCPs registered for domissanitary purposes in Brazil. OCP concentrations tended to be higher in summer than in winter. Dumping sites resulted in the highest OCP atmospheric concentrations and, thus, in the highest CR estimations. Despite of all limitations, probabilistic simulations suggested that people living in the studied regions are exposed to an increased risk of hepatic cancer. Infants and toddlers (0 < 2 y) were exposed to the highest inhalation CRs compared to other age groups. Other exposure pathways (such as ingestion and dermic uptake) are needed for a more comprehensive risk assessment. Moreover, this study also highlights the need to review the human exposure to OCPs through inhalation and their respective CR in other impacted areas worldwide, especially where high levels of OCPs are still being measured.

Biomonitoring mercury contamination using fur from roadkilled giant anteaters.

The giant anteater (Myrmecophaga tridactyla) can occur in both preserved and anthropogenic environments in Brazilian biomes. The Cerrado biome, where the samples were collected, is considered one of the world's biodiversity hotspots; however, a large part of it has been converted to pasture and agricultural land. In this environment, animals may be exposed to contaminants, such as mercury (Hg). Despite its immense biodiversity, there are few studies investigating Hg contamination in terrestrial mammals in Brazil. This study aimed to create a baseline for Hg levels in giant anteater fur and establish which biotic and abiotic variables can influence its concentration. Total Hg (THg) concentrations were determined by cold vapor atomic absorption spectrometry in 141 individuals sampled on highways between January and October 2017, in the state of Mato Grosso do Sul, Brazil. THg concentrations in fur ranged from 0.27 to 4.77 µg g -1. The decomposition stage of the carcasses and vehicular traffic volume on highways did not influence the THg concentrations. Juveniles presented lower THg concentrations than adults. A spatial pattern of higher concentrations in the eastern-southeastern region of the state was found, which could be related to anthropogenic impacts; however, no clear links have been established. The THg concentrations in giant anteaters' fur seems higher than expected considering the trophic position of the species. Despite this, the range was in accordance with studies of other Brazilian terrestrial mammals and within safe threshold levels. This study indicates the potential of utilizing roadkilled fauna to monitor large-scale contamination in wildlife.

Total mercury in wild felids occurring in protected areas in the central Brazilian Amazon

This is the first study to investigate mercury (Hg) contamination in felid species in the Brazilian Amazon. We collected 26 fur samples from wild felids of four species (Puma concolor, Panthera onca, Leopardus pardalis and Leopardus wiedii) occurring in the Mamirauá and Amanã sustainable development reserves, in the state of Amazonas. Samples were from museum specimens, except for five P. onca samples collected from free-living individuals. Total Hg concentrations ranged from 0.12 to 48.1 µg g-1. Concentrations of Hg did not differ significantly between museum specimens and live individuals of P. onca, but varied significantly among species, with significantly higher concentrations for P. onca and L. pardalis, which could be related to factors such as diet and habitat. (AU)

Air contamination by legacy and current-use pesticides in Brazilian mountains: An overview of national regulations by monitoring pollutant presence in pristine areas.

In the last decades, research regarding the dynamics of pesticides has grown, even in remote regions. Due to long-range atmospheric transport, environmental persistence and toxicological potential of organochlorine pesticides (OCPs), similar characteristics of current-use pesticides (CUPs) and their massive use in Brazil, these contaminants have become a major concern for environmental and human life. Thus, this study aimed to evaluate subgroups or individual chemicals of OCPs and CUPs, which could have travelled over two Conservation Unit sites in the Rio de Janeiro state. The study was carried out for 24 months, (2013-2015), in Itatiaia National Park (INP) and in the Serra dos Órgãos National Park (SONP), at ∼2400 and ∼2200 meters above sea level, respectively. The study was based on atmospheric passive sampling (polyurethane foam disks). Target pesticides were detected by means of gas chromatography device coupled with mass spectrometry (GC-MS). Significantly higher concentrations were measured in SONP when compared to INP. However, in broad terms, the contamination profile was quite similar for both national parks: The highest concentrations of endosulfan (INP - 1275 pg m-3 and SONP - 3202 pg m-3) were followed by cypermethrin (INP - 148 pg m-3 and SONP - 881 pg m-3) and chlorpyrifos (INP - 67 pg m-3 and SONP - 270 pg m-3). In agreement with previous studies, the atmospheric concentrations of legacy OCPs showed background air levels. The decrease of endosulfan over the years was highlighted with a parallel increase of chlorpyrifos, suggesting a collateral effect of the national bias of permissive and massive use of agrochemicals. CUPs seemed to behave like pseudo-persistent pollutants (pseudo-POPs). This is the first report of atmospheric concentrations of pyrethroids in Brazilian mountain regions, and possibly the first to investigate them in the air in South America or in any mountain region in the world.

Use of passive samplers to detect organochlorine pesticides in air and water at wetland mountain region sites (S-SE Brazil).

Low-density polyethylene (LDPE) passive samplers were deployed in upland surface waters and the overlying atmosphere during May and June 2012, to determine the transport and trends of freely dissolved and gaseous organochlorine pesticides (OCPs) along altitudinal gradients in mountain regions in south and southeast Brazil. Gaseous OCP concentrations were dominated by hexachlorobenzene (3.0-29 pg m(-3)) and endosulfans (Æ© = α-endosulfan + ß-endosulfan + endosulfan sulphate, 170-260 pg m(-3)), whereas freely dissolved endosulfans were significantly higher than all other OCPs (p < 0.001). The presence of some target pesticides at the highest elevation sites indicated their efficient high-altitude transport from regional sources. Air-water exchange gradients indicated net deposition of most volatile and recently banned OCPs (e.g., HCB, endosulfan) over Brazilian mountains. Moreover, the exposure of these sites to large-scale continental airflows with varying source contributions may partly explain the atmospheric deposition of selected OCPs over upland freshwaters at tropical and subtropical mountains sites in Brazil. These findings, coupled with LDPE passive air and water sampling measurements, point out the potential inputs from distant sources of semi-volatile chemicals to the two high-altitude sites.

Bulk atmospheric deposition of persistent toxic substances (PTS) along environmental gradients in Brazil.

Bulk atmospheric deposition measurements for selected persistent toxic substances (PTS) were performed along environment gradients (urban-suburban-rural-background sites) in Brazil. The aim with this work is to investigate the fate of PTS and their emissions in South America, particularly along environment transects. Bulk sampler systems (polyurethane foams, 1 × 1 m(2)) were fixed along environment gradients (urban-suburban-rural-background) over summer and winter periods (2005-2007) at sites of different climate zones of Brazil. Organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) were analyzed by gas chromatography coupled to electron capture detector (Shimadzu 2010, 20i GC-ECD). Urban sites reported the highest deposition rates for all PTS, ranging from tens to thousands of pictograms per square meter per day. Basically, there were no obvious seasonal differences in deposition rate concentrations for PTS along the urban-suburban-rural-background gradient. Dichlorodiphenyltrichloroethane (DDT) and its metabolites were the OCs most frequently detected at relatively high deposition rate levels (>1,000 pg m(-2) day(-1)). Other legacy and current-use pesticides such as hexachlorocyclohexanes, endosulfans, hexachlorcyclobenzine, dieldrin, aldrin, metoxichlor, and chlodanes were also detected at lower deposition rate levels (10-100 pg m(-2) day(-1)). PCBs were detected at extremely high deposition rate levels (1,000-10,000 pg m(-2) day(-1)) with highest contributions from the tetra-PCBs (PCB-52, PCB-44, PCB-66, PCB-81, and PCB-77) and penta-PCB congeners (PCB-101, PCB-105, PCB-114, PCB-118, and PCB-126). The greatest deposition rate concentrations for total PCBs were mainly detected at urban sites in connection with high population densities. The observed high deposition rate concentrations for PCBs and DDTs at urban sites are probably associated with old PTS stocks emissions. For PCBs in particular, the high levels are strongly associated with local population densities, highlighting the effect of local/regional urban sources on these target PTS. These results are important to show that even though the use of PTS is regulated, the deposition of selected PTS is still impacted by local and regional emissions in Brazil and may be related to the historical and continued emissions from old PTS stocks.

Organochlorine pesticides (OCs) and polychlorinated biphenyls (PCBs) in sediments and crabs (Chasmagnathus granulata, Dana, 1851) from mangroves of Guanabara Bay, Rio de Janeiro State, Brazil.

Organochlorinated compounds, seven indicator PCB congeners, DDT and its main metabolites, were determined in sediment and crab (Chasmagnathus granulata) samples collected from mangrove areas near Rio de Janeiro, Brazil. Samples were analysed according to the FAO/SIDA protocols using continuous non-polar solvent extraction and a conventional GC-ECD apparatus. The highest levels of total PCB congeners and total DDT metabolites in sediments (184.16 and 37.40 ng g(-1)d.w. respectively) and crab eggs (570.62 and 98.22 ng g(-1)d.w. respectively) were found at impacted mangroves. The higher PCB congeners than DDT metabolites levels suggesting a stronger industrial impact in this area. The results indicate that the population density of crab is negatively affected by sediment contamination that is reflected basically by the organochlorine content in the female eggs. The organochlorine concentration in eggs is more significant to evaluate or estimate an impact of these pollutants upon C. granulata population than the organochlorine concentration in sediment samples.

DDT and its metabolites in breast milk from the Madeira River basin in the Amazon, Brazil.

Until the 1990s the 1,1,1-trichloro-bis-2,2'-(4chlorophenyl) ethane (DDT) was sprayed in the walls of the house along the Madeira River basin, Brazilian Amazon, a region well known for its large number of malaria cases. In 1910, Oswaldo Cruz described the presence of malaria in 100% of the population living in some localities from the Madeira River basin. Data available in the literature point to the DDT contamination in fishes captured in Madeira River region. Fish is the major source of dietary protein to these people. DDT tends to accumulate in lipid rich tissues and is being eliminated by different events, including lactation. Considering the importance of feeding breast milk to the children, the associated risks of DDT exposure via breast milk intake to children must be assessed. This is the main objective of this work: to analyse the presence of the p,p'-DDT and its metabolites p,p'-DDE and p,p'-DDD in 69 human milk samples and to estimate the intake of DDT and its metabolite in terms of total DDT (total DDT=p,p'-DDE+p,p'-DDD+p,p'-DDT). All the samples showed contamination with DDT and its metabolites ranging from 25.4 to 9361.9 ng of total DDT/g of lipid (median=369.6 ng of total DDT/g of lipid) and 8.7% of the estimated daily intake (EDI), in terms of total DDT, which was higher than the acceptable daily intake proposed by the WHO.

Polycyclic aromatic hydrocarbons assessment in sediment of national parks in southeast Brazil.

The aim of this work was to assess the levels of polycyclic aromatic hydrocarbons (PAHs) in the environment and their sources found in protected regions of southeastern Brazil. Samples of sediments were collected at four National Parks: Itatiaia National Park (PNIT), Serra da Bocaina National Park (PNSB), Serra dos Orgãos National Park (PNSO) and Jurubatiba National Park (PNJUB). The National Parks studied comprise rainforests, altitudinal fields and 'restinga' environments located in the Minas Gerais, Rio de Janeiro and São Paulo states. The sampling was conducted between 2002 and 2004 from June to September. In general, the environmental levels of PAHs found were similar to those in other remote areas around the globe. PNIT exhibited the highest median values of total PAHs in sediment (97 ng g(-1)), followed by PNJUB (89 ng g(-1)), PNSO (57 ng g(-1)) and PNSB (27 ng g(-1)). The highest levels of total PAHs (576 and 24430 ng g(-1)) could be associated to a point source contamination where are characterized for human activities. At PNSB and PNIT the PAH profiles were richer in 2 and 3 ring compounds, whereas at PNSO and PNJUB, the profiles exhibited 3 and 4 ring compounds. The phenanthrene predominance in most samples could indicate the influence of biogenic synthesis. The samples with a petrogenic pattern found in this study might be associated with the vicinity of major urban areas, highway traffic and/or industrial activities close to PNSO and PNIT. At PNIT and PNJUB, forest fires and slash and burn agricultural practices may drive the results towards a pyrolytic pattern.

Persistent organic pollutants in atmospheric deposition and biomonitoring with Tillandsia usneoides (L.) in an industrialized area in Rio de Janeiro state, southeast Brazil--Part II: PCB and PAH.

Monitoring of immission of persistent organic pollutants in the industrialized area of Volta Redonda (V.R.) and in the National Park of Itatiaia (PNI) in southeast Brazil was performed using an endemic bromeliad species as biomonitor and measuring bulk deposition rates of polychlorinated biphenyls (PCB) and polycyclic aromatic hydrocarbons (PAH). For the sum of PCB, overall deposition rates were between 17 and 314 ng/(m2 day) in winter and between 43 and 81 ng/(m2 day) in summer, respectively. Deposition rates of dioxin-like PCBs ranged from 0.14 to 2.8 pg WHO-TEQ/(m2 day) in winter and from 0.90 to 4.3 pg WHO-TEQ/(m2 day) in summer. PCB deposition rates (total PCB and WHO-TEQ) were in the same range in winter in V.R. and PNI. In summer, contamination levels in V.R. were 6-10-folds higher than in PNI. PCB concentrations in biomonitor samples from V.R. and PNI were in the same range in summer and in winter. Concentrations of total PCB ranged from 14 to 95 microg/kg dry matter (d.m.) in winter and from 18 to 27 microg/kg d.m. in summer, respectively. The TEQ values were between 1.7 and 4.1 ng WHO-TEQ/kg d.m. in winter and between 1.9 and 2.9 ng WHO-TEQ/kg d.m. in summer. PCB concentrations of di-ortho PCB but not of non-ortho PCB were a factor of 2-4 lower in summer in both areas. PCB congener profiles resembled those from technical formulations. The profiles shifted to the higher chlorinated congeners in summer, probable due to revolatilisation of the lighter components at higher temperatures. PCB profiles in biomonitor resembled those from deposition samples and the shift to the heavier congeners in summer was even more pronounced. PAH deposition rates were in a similar range in both areas (131-2415 ng/(m2 day)). PAH levels in biomonitor samples from V.R. were about one order of magnitude higher than in samples from PNI indicating the impact of local sources. PAH profiles revealed stationary thermal processes as main source of contamination in V.R. whereas in PNI, biomass burning seems to be the main contamination source.