Residues of legacy organochlorine pesticides and DDT metabolites in highly consumed fish from the polluted Guanabara Bay, Brazil: distribution and assessment of human health risk.

Organochlorine (OCP) pesticides were determined in samples of sardine (Sardinella brasiliensis), whitemouth croaker (Micropogonias furnieri), and mullet (Mugil liza) from Guanabara Bay (state of Rio de Janeiro, Brazil). OCP concentrations and fish consumption were linked with acceptable daily intake values in order to assess the human health risk for the Brazilian population. The total concentrations of OCPs (Σ OCP) was 6.6 ng/g f.w., 7.5 ng/g f.w., and 2.8 ng/g f.w. for sardines, corvina, and mullet, respectively. There was a significant difference (P < 0.05) among the species related to o,p'-DDD and o,p'-DDT concentrations. Both DDT-related compounds were 5 and 76 times more abundant in sardines than in whitemouth croaker and mullet. Newly discovered DDT metabolite, o-Cl-DDMU, was frequently detected in the fish. None of the samples exceeded the maximum limits for acceptable levels of OCP residues. According to the data of average intake of Brazilian population, none of three species exceeded toxicological parameter. The investigated fishes are considered as safe for human consumption in regard to exposure of the studied OCPs. However, fish may be a intake source of OCP metabolites such as o-Cl-DDMU whose toxicity is still unknown.

First assessment of persistent organic pollutants and halogenated natural compounds in an omnivorous resident coral-reef fish species, black triggerfish, Melichthys niger, from an Atlantic oceanic island, Brazil.

Studies on the occurrence of POPs and other persistent compounds in pristine areas are extremely valuable, as they offer insights on the long-range transportation of POPs and the occurrence of natural compound producers' areas. In this regard, this study aimed to report data of both anthropogenic (polychlorinated biphenyls, PCBs, and polybrominated diphenyl ethers, PBDEs) and natural (methoxylated PBDEs, MeO-BDEs) compounds in tissues of the black triggerfish, Melichthys niger (Tetraodontiformes, Balistidae), specimens (n = 30) sampled in 2018 during a scientific expedition conducted at Trindade Island. Concentrations of ∑28PCBs ranged from 73 to 1052 ng g-1 lw in liver, 334 to 1981 ng g-1 lw in gonads, and 20 to 257 ng g-1 lw in muscle, with the predominance of PCB-180 in liver and PCB-52 in gonad and muscle. Concentrations of ∑7PBDEs ranged from

Reduced plasma zinc levels, lipid peroxidation, and inflammation biomarkers levels in hemodialysis patients: implications to cardiovascular mortality.

Despite the fact that low plasma zinc (Zn) levels play important roles in the oxidative stress, the relationships between lipid peroxidation and inflammation biomarkers with low plasma Zn levels have not been investigated in chronic kidney disease (CKD) patients. The aim of this study was to evaluate the Zn plasma levels, electronegative LDL [LDL(-)] levels, and inflammation markers as predictors of cardiovascular (CV) mortality in hemodialysis (HD) patients. Forty-five HD patients (28 men, 54.2 ± 12.7 years, 62.2 ± 51.4 months on dialysis and BMI 24.3 ± 4.1 kg/m(2)) were studied and compared to 20 healthy individuals (9 men, 51.6 ± 15.6 years, BMI 25.2 ± 3.9 kg/m(2)) and followed for 24 months to investigate the risks for CV mortality. LDL(-) levels were measured by ELISA, plasma Zn levels by atomic absorption spectrophotometry, C-reactive protein (CRP) level by immunoturbidimetric method, and tumor necrosis factor-α (TNF-α), interleukin-6 (IL-6), monocyte chemotactic protein-1 (MCP-1), and plasminogen activator inhibitor-1 (PAI-1) levels by a multiplex assay kit. HD patients presented low plasma Zn levels (54.9 ± 16.1 µg/dL) and high-LDL(-) (0.18 ± 0.12 U/L) and TNF-α (5.5 ± 2.2 pg/mL) levels when compared to healthy subjects (78.8 ± 9.4µ g/dL, 0.10 ± 0.08U/L, 2.4 ± 1.1 pg/mL, respectively, p < 0.05). Zn plasma levels were negatively correlated to TNF-α (r = -0.49; p = 0.0001) and LDL(-) (r = -0.33; p = 0.008). During the 2 years, 24.4% of the patients died, all due to CV disease. Analysis by the Cox model showed that high CRP, TNF-α, IL-6 levels, and long duration of HD were significant predictors of mortality. In conclusion, reduced Zn levels were associated with lipid peroxidation and inflammation, and we confirm here in a Brazilian cohort of HD patients that inflammation markers are strong predictors of CV death.

Mercury levels in feed and muscle of farmed tilapia.

BACKGROUND: Fish consumption is considered the most important source of contaminant exposure for humans beings, and farmed fish can be exposed to contaminants via feed supply. METHODS: Total mercury concentrations (THg) were determined in the muscle, liver, and feed of farmed Nile tilapia (juveniles and adults) from four different fish farms in Brazil (net cages and intensive tanks systems), by a flow injection mercury system. RESULTS: Mercury concentrations observed in fish muscle were markedly lower (13.5-30.5 µg kg(-1)) than the values recommended by ANVISA/MAPA for edible part of fish (500 µg kg(-1)), and in the liver the concentrations found were higher than in the muscle. CONCLUSIONS: These low levels of THg in farmed tilapia may be due to the low THg concentrations found in the analyzed fish feed, that ranged from 5.2 to 33.2 µg kg(-1), below the limit of 100 µg kg(-1) established by the European Commission.

Greenhouse gas emissions from the Brazilian Antarctic Station "Comandante Ferraz".

BACKGROUND: Climate change is a natural phenomenon that has been intensified due to increased emissions of greenhouse gases (GHG). It has become an indispensable issue in international negotiations related to global sustainability and is deeply related to the overall status of environmental health in our planet. METHODS: We compiled an inventory of GHG emissions that resulted from human activities at the Brazilian Antarctic Scientific Station "Comandante Ferraz" (EACF) and collected emissions data relating to these activities from January to March 2011. The present work aims to identify the sources of GHG emissions, their characteristics, and composition, using as methodology and framework basis the international ISO 14,064:07 and the GHG Protocol. RESULTS: We addressed emissions of CO(2), CH(4), and N(2)O arising from the use of vehicles, diesel-electric generators, boilers, and wastewater treatment for the sewage treatment plant. We identified that the main GHG emissions derived from the activities of power generation using diesel and boilers (more than 80% of the emissions), adding more than 772 t of CO(2) equivalents. CONCLUSIONS: We identified that the diesel generators and boilers are the most important sources of emission by Expedition XXIX (2010-2011). In that CO(2) is principally emitted in relation to electrical energy generation from diesel generators, we emphasize the need for fuel burning reduction through energy consumption reduction.

Association between circulating electronegative low-density lipoproteins and serum ferritin in hemodialysis patients: a pilot study.

BACKGROUND: Iron supplementation is a common recommendation to chronic kidney disease patients undergoing hemodialysis (HD). However, iron excess is closely associated with lipid peroxidation and, it is well known that electronegative low-density lipoproteins (LDL[-]) are present at higher plasma concentrations in diseases with high cardiovascular risk such as chronic kidney disease. Thus, the aim of this study was to investigate whether ferritin levels are associated with LDL(-) levels in HD patients. DESIGN: This was a cross-sectional study. SETTING: This study was conducted from a private clinic in Rio de Janeiro, Brazil. PATIENTS: The study included 27 HD patients and 15 healthy subjects. METHODS AND PROCEDURES: Twenty-seven HD patients (14 men, 58.6 ± 10 years, 62.2 ± 51.4 months on dialysis, and body mass index: 24.4 ± 4.2 kg/m(2)) were studied and compared with 15 healthy individuals (6 men, 53.8 ± 15.4 years, body mass index: 24.5 ± 4.3 kg/m(2)). Serum LDL(-) levels were measured using the enzyme-linked immunosorbent assay method; ferritin levels by commercially available kits, and tumor necrosis factor-α, interleukin-6, monocyte chemoattractant protein-1, and plasminogen activator inhibitor-1 were determined with a multiplex assay kit manufactured by R&D Systems. RESULTS: The HD patients presented higher LDL(-) and tumor necrosis factor-α levels (0.15 ± 0.13 U/L and 5.9 ± 2.3 pg/mL, respectively) than healthy subjects (0.07 ± 0.05 U/L and 2.3 ± 1.3 pg/mL, respectively) (P = .0001). The mean ferritin level in HD patients was 1,117.5 ± 610.4 ng/mL, and 90% of patients showed ferritin levels exceeding 500 ng/mL. We found a positive correlation between LDL(-) and ferritin in the patients (r = 0.48; P = .01), and ferritin was a significant contributor to LDL(-) concentrations independent of inflammation. CONCLUSIONS: Excess body iron stores for HD patients was associated with signs of increased oxidative stress, as reflected by increased LDL(-) levels in HD patients.

Inventory approach for short-chain chlorinated paraffins for the Stockholm Convention implementation in Brazil.

Chlorinated paraffins (CPs) are chemicals with multipurpose applications. Their global production has increased despite their adverse impacts on the environment and human health. In 2017, short-chain chlorinated paraffins (SCCPs) were listed as persistent organic pollutants (POPs) in the Stockholm Convention. Yet, specific exemptions were granted for their applications despite the recycling prohibition for products containing SCCPs. Therefore, we aimed to produce the first Brazilian inventory of SCCPs following its respective guidance to evaluate the applicability of the SCCP inventory guidance and to provide technical insights regarding SCCPs in the update of the Brazilian National Implementation Plan (NIP). Moreover, we performed a review of SCCP occurrence in Brazil to fulfil data gaps in the inventory development. We identified and consulted nationwide stakeholders and assessed foreign trade data of CPs and products that might contain CPs in relevant amounts. The Brazilian production of CPs was discontinued in 1994. However, CPs are still imported and used in the country. CPs have been mostly applied as plasticizers, flame retardants and lubricants in Brazil. The import of products containing CPs also pose a significant route of CP entrance into Brazil. Thus, the current end-of-life management of CP-containing products is a bottleneck towards the Convention implementation. The guidance application was feasible and useful despite the low engagement of stakeholders. To assess foreign trade of CPs and CP-containing products, we recommend the use of more specific tracking codes. Besides, the review of SCCP occurrence is not a demanded part for an inventory but was a useful complementation.

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.

Equatorial Atlantic pelagic predators reveal low content of PBDEs in contrast to MeO-BDEs: An analysis of brominated diphenyl ethers in blue shark and yellowfin tuna.

Polybrominated diphenyl ethers (PBDEs) and their methoxylated analogues (MeO-BDEs) are widely distributed in the environment. The main concern about the presence of PBDEs and MeO-BDEs in fish is due to their potential endocrine disruption effects in the specimens, and their potential risk to the health of human consumers. Considering these concerns, the goal of this study was to investigate the occurrence of PBDEs and MeO-BDEs in muscle tissues of blue shark (BSH), Prionace glauca, and yellowfin tuna (YFT), Thunnus albacares, caught in the Equatorial Atlantic Ocean (EAO), North-eastern Brazilian waters, and to evaluate the potential risk of human exposure by consumption. Muscle tissues of YFT and BSH were extracted using a Soxhlet apparatus and an Accelerated Solvent Extractor (ASE), respectively. PBDEs and MeO-BDEs were analysed by GC-NCI-MS. Concentrations of PBDEs ranged from not detected (nd) to 10 ng g-1 lipid weight (lw) in YFT muscle samples, while PBDE levels in BSH muscle samples ranged from

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.

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.

Tracking mercury in the southwestern Atlantic Ocean: the use of tuna and tuna-like species as indicators of bioavailability.

Mercury is a trace element that is potentially dangerous due its high toxicity and tendency to bioaccumulate in organisms. Currently, high mercury concentrations are seen in the environment especially due climate changes. Studies regarding mercury bioavailability in the southwestern Atlantic Ocean using tuna and tuna-like species are rare. The aim of the present study was to use tuna and tuna-like species (Thunnus atlanticus, Thunnus albacares, Katsuwonus pelamis, Euthynnus alletteratus, Coryphaena hippurus and Sarda sarda) as indicators of the availability of total mercury (THg) in oceanic food webs of the southwestern Atlantic Ocean. THg concentrations varied significantly among species for both muscle and liver (Kruskal-Wallis test; H5,130 = 52.7; p < 0.05; H5,130 = 50.1; p < 0.05, respectively). The lowest concentrations were found in C. hippurus (0.008 mg kg-1 wet weight in the muscle and 0.003 mg kg-1 wet weight in the liver), and the highest concentrations were reported in the muscle of T. atlanticus (1.3 mg kg-1 wet weight) and in the liver of S. sarda (2.5 mg kg-1 wet weight). The continued monitoring of tuna and tuna-like species is necessary to assist in their conservation since tuna can be sentinels of mercury pollution.

Biological factors affecting total mercury and methylmercury levels in Antarctic penguins.

Penguins in Antarctica occupy high trophic levels, thus accumulating high amounts of mercury (Hg) through bioaccumulation and biomagnification. Blood reflects the current levels of contaminants circulating in the body, while feathers are known as the main route of Hg elimination in birds. Studies sampling chicks and adults can provide a comprehensive picture of bioaccumulation and local contamination. Three pygoscelid species (Pygoscelis adeliae, Pygoscelis antarcticus and Pygoscelis papua) have circumpolar distributions being the ideal sentinels of Antarctic environmental pollution. This study aimed to assess Hg contamination of the pristine Antarctic region using non-destructive penguin samples. Fieldwork was carried out during the austral summer of 2013/2014 in the South Shetland Islands, off the north-west Antarctic Peninsula. Concentrations of total Hg (ng.g-1 dw) in blood ranged from 39 to 182 in chicks and 45 to 581 in adults, while concentrations in feathers ranged from 73 to 598 in chicks and 156 to 1648 in adults. Most Hg in feathers (about 70%) is accumulated in the form of methylmercury. Differences were demonstrated in mercury bioaccumulation were related to species and age, but not to sex. To our knowledge this is the first study to report MeHg levels in both juvenile and adult pygoscelid penguins.

Laboratory and field tests for risk assessment of metsulfuron-methyl-based herbicides for soil fauna.

Metsulfuron-methyl is one of the most used sulfonylurea herbicides, being applied alone in pre-emergence and with a mineral oil (as adjuvant) in post-emergence. In risk assessment of pesticides, ecotoxicity tests have been applied to assess the effects of products and mixtures under laboratory conditions, but they are limited in their ecological relevance when compared to field assessments. Considering the differences between laboratory and field exposure, and the lack of data on the effects of metsulfuron-methyl in natural soils, this study consisted in a set of tests to assess the ecotoxicity of this herbicide applied alone, combined with an adjuvant (mineral oil) and the adjuvant applied alone, both under laboratory and field exposure, with artificial and natural soil respectively. Reproduction tests with four non-target soil invertebrates species were performed in laboratory, while two experiments were performed in field evaluating avoidance behaviour, feeding activity, mesofauna abundance and pesticide residual. Laboratory results showed that metsulfuron-methyl alone is not a threat to soil fauna on the recommended doses. However, the presence of mineral oil as adjuvant showed ecotoxicity to Eisenia andrei, Enchytraeus crypticus and Proisotoma minuta on laboratory tests. Field evaluations indicated that metsulfuron-methyl and the adjuvant do not impaired the feeding activity of the soil fauna. The low abundance of native communities could be related to soil management. Results showed that laboratory and field evaluations are necessary to better understanding of the effects of pesticides to soil fauna and adjuvant addition should be considered on pesticides risk assessment.

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.

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.

Dioxin- and POP-contaminated sites--contemporary and future relevance and challenges: overview on background, aims and scope of the series.

BACKGROUND, AIM AND SCOPE: Once they have been generated, polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) and other persistent organic pollutants (POPs) can persist in soils and sediments and in waste repositories for periods extending from decades to centuries. In 1994, the US EPA concluded that contaminated sites and other reservoirs are likely to become the major source of contemporary pollution problems with these substances. With this in mind, this article is the first in a new series in ESPR under the title 'Case Studies on Dioxin and POP Contaminated Sites--Contemporary and Future Relevance and Challenges', which will address this important issue. The series will document various experiences from sites contaminated with PCDD/F and other POPs. This article provides an overview of the content of the articles comprising the series. In addition, it provides a review of the subject in its own right and identifies the key issues arising from dioxin/POP-contaminated sites. Additionally, it highlights the important conclusions that can be drawn from these examples. The key aim of this article and of the series as a whole is to provide a comprehensive overview of the types of PCDD/F contaminated sites that exist as a result of historical activities. It details the various processes whereby these sites became contaminated and attempts to evaluate their contemporary relevance as sources of PCDD/Fs and other POPs. It also details the various strategies used to assess these historical legacies of contamination and the concepts developed, or which are under development, to effect their remediation. MAIN FEATURES: Special sessions on 'Contaminated sites--Cases, remediation, risk and policy' were held at the DIOXIN conferences in 2006 and 2007, and this theme will be continued at DIOXIN 2008 to be held in Birmingham. Selected cases from the approximately 70 contributions made to these sessions, together with some additional invited case studies are outlined together with the key issues they raise. By evaluating these cases and adding details of experiences published in the current literature, an overview will be given of the different features and challenges of dioxin and POP-contaminated sites. RESULTS: This article provides a systematic categorisation of types of PCDD/F and POP-contaminated sites. These are categorised according to the chemical or manufacturing process, which generated the PCDD/Fs or POPs and also includes the use and disposal aspects of the product life cycle in question. The highest historical PCDD/F and dioxin-like polychlorinated biphenyl (PCB) contamination burdens have arisen as a result of the production of chlorine and of chlorinated organic chemicals. In particular, the production of chlorinated pesticides, PCBs and the related contaminated waste streams are identified being responsible for historical releases of toxic equivalents (TEQs) at a scale of many tonnes. Along with such releases, major PCDD/F contaminated sites have been created through the application or improper disposal of contaminated pesticides, PCBs and other organochlorine chemicals, as well through the recycling of wastes and their attempted destruction. In some extreme examples, PCDD/F contaminated sites have also resulted from thermal processes such as waste incinerators, secondary metal industries or from the recycling or deposition of specific waste (e.g. electronic waste or car shredder wastes), which often contain chlorinated or brominated organic chemicals. The examples of PCDD/F and dioxin-like PCB contamination of fish in European rivers or the impact of contaminated sites upon fishing grounds and upon other food resources demonstrate the relevance of these historical problems to current and future human generations. Many of the recent food contamination problems that have emerged in Europe and elsewhere demonstrate how PCDD/F and dioxin like PCBs from historical sources can directly contaminate human and animal feedstuffs and indeed highlight their considerable contemporary relevance in this respect. Accordingly, some key experiences and lessons learnt regarding the production, use, disposal and remediation of POPs from the contaminated sites are summarised. DISCUSSION: An important criterion for evaluating the significance and risks of PCDD/Fs and other POPs at contaminated sites is their present or future potential for mobility. This, in turn, determines to a large degree their propensity for off-site transport and environmental accessibility. The detailed evaluation of contaminated site cases reveals different site-specific factors, which influence the varied pathways through which poor water-soluble POPs can be mobilised. Co-contaminants with greater water solubility are also typically present at such sites. Hence, pumping of groundwater (pump and treat) is often required in addition to attempting to physically secure a site. At an increasing number of contaminated sites, securing measures are failing after relatively short time spans compared to the time horizon, which applies to persistent organic pollutant contamination. Due to the immense costs and challenges associated with remediation of contaminated sites 'monitored natural attenuation' is increasingly gaining purchase as a conceptual remediation approach. However, these concepts may well prove limited in their practical application to contaminated sites containing persistent organic pollutants and other key pollutants like heavy metals. CONCLUSIONS: It is inevitable, therefore, that dioxin/POP-contaminated sites will remain of contemporary and future relevance. They will continue to represent an environmental issue for future generations to address. The securing and/or remediation of dioxin/POP-contaminated sites is very costly, generally in the order of tens or hundreds of millions of dollars. Secured landfills and secured production sites need to be considered as constructions not made for 'eternity' but built for a finite time scale. Accordingly, they will need to be controlled, supervised and potentially repaired/renewed. Furthermore, the leachates and groundwater impacted by these sites will require ongoing monitoring and potential further remediation. These activities result in high maintenance costs, which are accrued for decades or centuries and should, therefore, be compared to the fully sustainable option of complete remediation. The contaminated site case studies highlight that, while extensive policies and established funds for remediation exist in most of the industrialised western countries, even these relatively well-regulated and wealthy countries face significant challenges in the implementation of a remediation strategy. This highlights the fact that ultimately only the prevention of contaminated sites represents a sustainable solution for the future and that the Polluter Pays Principle needs to be applied in a comprehensive way to current problems and those which may emerge in the future. RECOMMENDATIONS AND PERSPECTIVES: With the continuing shift of industrial activities in developing and transition economies, which often have poor regulation (and weak self-regulation of industries), additional global challenges regarding POPs and other contaminated sites may be expected. In this respect, a comprehensive application of the "polluter pays principle" in these countries will also be a key to facilitate the clean-up of contaminated areas and the prevention of future contaminated sites. The threats and challenges of contaminated sites and the high costs of securing/remediating the problems highlight the need for a comprehensive approach based upon integrated pollution prevention and control. If applied to all polluting (and potentially polluting) industrial sectors around the globe, such an approach will prove to be both the cheapest and most sustainable way to underpin the development of industries in developing and transition economies.

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.

Polycyclic aromatic hydrocarbons in the South American environment.

Pollution of the environment with polycyclic aromatic hydrocarbons (PAHs) should be a global concern, especially in urbanized areas. In South American countries, where notable increase in urban populations has been observed in the past few years, reliable information about the pollution status of these urban environments is not always easily accessible, and therefore an effort to collect updated information is required. This review attempts to contribute by analyzing the existing information regarding environmental levels of PAHs in some South American countries. A regional trend for environmental PAH information is an uneven contribution, because some countries, such as Bolivia, Peru, Paraguay, and Ecuador, have reported no information at all in the scientific literature, reflecting to a certain extent the different patterns of economic, technical, and scientific development. PAH air monitoring is one of the areas that has received the most attention during the last few years, mainly in Brazil, Chile, and Argentina, where data represent a few geographical areas within the region. PAH levels in air from some urban areas in Argentina, Brazil, and Chile, considered moderate to high (100-1000ng/m3), are probably among the highest values reported in the open literature. Urbanization, vehicle pollution, and wood fires are the principal contributors to the high reported levels. In more temperate areas, a clear distinction is observed between summer and winter levels. PAH monitoring in soils is very limited within the region, with few data available, and most information indicates widespread pollution. In Brazil, values for many representative ecosystems were found. In Chile, data from forestry and agricultural areas indicate in general low concentrations, in spite of a relatively high detection frequency. Pollution levels in soils are highly dependent on their closeness to PAH sources and certain cultural practices (agricultural burnings, forest fires, etc.). Water PAH levels are rarely reported in the scientific literature for South American countries. Few data were available, even though many regulatory agencies perform routine analysis of hydrocarbons in waters. No information was found specifically related to PAH compounds, which could indicate generally low PAH levels in waters. Regional PAH information for sediments also indicates higher levels. Overall, as observed for water, sediment data indicate a complex situation in densely populated areas affected by urban-industrial inputs where high PAH levels are found. In contrast, in remote areas a typical profile of diagenetic PAHs dominates. Concentrations are greatly variable and are principally related to several highly contaminated sites in Argentina and Brazil (hot spots) with levels four to five orders of magnitude higher. Even though PAHs have carcinogenic properties, little attention has been paid to the analysis of aquatic organisms except in the case of bivalves. As observed for other environmental receptors, the regional data distribution is uneven and is heavily centered in coastal environments and in a few countries (Argentina, Brazil, Chile, and Peru). The most comprehensive PAH monitoring program in the South American coastal environment is the Mussel Watch. Baseline PAH concentrations range from 200 to 700 microg kg(-1) lipids in unpolluted sites; from 1,000 to 3,000 microg kg(-1) in moderately contaminated sites; and from 4,000 to 13,000 microg/kg lipids in the most affected bivalves that come from areas of Río de la Plata (Argentine side), Recife (Brazil), and Punta Arenas (Chile). Critical data gaps exist with respect to PAH analysis in biota, including humans, in foodstuffs, and subsequent effects. Considering the high levels reported in the air compartment, risk assessment procedures in highly populated areas need to be performed. Additionally, few countries within the region have information on PAH levels. In these countries, this type of analysis needs to be performed, and the laboratory capacity needs to be built to assure the accomplishment of these objectives.

Polychlorinated biphenyls and DDT in swordfish (Xiphias gladius) and blue shark (Prionace glauca) from Brazilian coast.

The polychlorinated biphenyls (PCBs) and DDT may bioaccumulate in the aquatic food web and have been of great concern due to their toxic effects on wildlife and human health. There is evidence showing that fish in the human diet contributes at a significant proportion to the total intake of PCBs and other organochlorine compounds, particularly fish with higher fat levels. This study investigated the concentration of PCBs and DDTs in muscle tissues of samples of the blue shark (Prionace glauca) and a swordfish (Xiphias gladius) from east Brazilian coast and estimate the human exposure to total DDTs through the consumption of both the species. Samples of the each species were caught between August and September 2001. The mean concentration for summation operator PCBs in P. glauca was 3.15 ng/g w.w. and the summation operator DDTs was 0.93 ng/g w.w. The mean concentration of summation operator PCBs in X. gladius was 6.50 ng/g and the mean of summation operator DDTs was 2.47 ng/g. The estimated daily intake of summation operator DDT through X. gladius or P. glauca consumption can be considered safe since it contributes to less than 0.1% of the limit of acceptable daily intake (ADI) of summation operator DDT proposed by WHO.